WASHINGTON — Internal State Department emails and documents released late Friday further implicate Secretary of State Mike Pompeo in a campaign orchestrated this year by President Trump and his personal lawyer Rudolph W. Giuliani to pressure Ukraine for political favors.

The emails indicate that Mr. Pompeo spoke at least twice by telephone with Mr. Giuliani in March as Mr. Giuliani was urging Ukraine to investigate Mr. Trump’s rivals, and trying to oust a respected American ambassador to Ukraine, Marie L. Yovanovitch, who had been promoting anticorruption efforts in the country. Mr. Pompeo ordered Ms. Yovanovitch’s removal the next month. The first call between Mr. Giuliani and Mr. Pompeo was arranged with guidance from Mr. Trump’s personal assistant, the documents suggest.

The documents also show that the State Department sent members of Congress a deliberately misleading reply about Ms. Yovanovitch’s departure after they asked about pressure on her. As part of the effort to oust her, Mr. Giuliani and his associates encouraged news outlets favorable to the president to publicize unsubstantiated claims about Ms. Yovanovitch’s disloyalty to Mr. Trump.

The documents, and recent congressional testimonies in the impeachment inquiry, tie Mr. Pompeo closely to efforts by Mr. Trump and Mr. Giuliani to persuade the Ukrainian government to announce investigations that could help Mr. Trump politically. Those include investigations into the family of former Vice President Joseph R. Biden Jr., a Democratic presidential candidate, and claims that Ukrainian officials worked to undermine Mr. Trump’s 2016 campaign. As Mr. Trump sought those investigations, he and his team held up $391 million of military aid critical to Ukraine — which is in a grinding war against Russian-backed separatists — and a coveted White House meeting.

The release of the documents, obtained by a liberal watchdog group that had filed a public records request, came as Mr. Pompeo refused to voluntarily hand over State Department documents about Ukraine to the House committees leading the impeachment inquiry. Representative Adam B. Schiff, the chairman of the House Intelligence Committee, said on Wednesday that Mr. Pompeo was engaged in a Watergate-style “obstruction of this investigation.”

The State Department released the documents in response to a lawsuit brought by the liberal watchdog, American Oversight, whose founders include lawyers who worked in the Obama administration.

Austin Evers, the executive director of the group, said that the documents revealed “a clear paper trail from Rudy Giuliani to the Oval Office to Secretary Pompeo to facilitate Giuliani’s smear campaign against a U.S. ambassador.”

Mr. Pompeo has refused to answer questions about his role in the Ukraine affair. The State Department did not reply on Saturday to detailed questions about the documents or witness testimonies in the inquiry that put the secretary at the center of the matter.

The documents bolstered testimony delivered Wednesday by Gordon D. Sondland, the American ambassador to the European Union and a player in the pressure campaign on Ukraine. He told lawmakers in a public hearing that Mr. Pompeo had full knowledge of the campaign and even approved certain hard-line tactics. Mr. Pompeo and his top aides “knew what we were doing, and why,” Mr. Sondland said, noting that “everyone was in the loop.” He recited email exchanges he had had with Mr. Pompeo on the pressure campaign.

Last month, Mr. Pompeo acknowledged he took part in the July 25 telephone call between Mr. Trump and President Volodymyr Zelensky of Ukraine.

The documents, testimony and interviews with Mr. Giuliani paint a portrait of a secretary of state who not only had intimate knowledge of the pressure campaign against Ukraine and the effort to undermine and remove a respected ambassador, but took part in her ouster despite warnings about the campaign from lawmakers and a half-dozen former ambassadors to Ukraine.

The emails released Friday show that Mr. Giuliani’s assistant reached out to Mr. Trump’s assistant seeking “a good number” for Mr. Pompeo. “I’ve been trying and getting nowhere through regular channels,” Mr. Giuliani’s assistant wrote. Mr. Trump’s assistant forwarded the inquiry to a State Department official, and the first call between Mr. Giuliani and Mr. Pompeo took place within days, the emails show.

The emails also show that Mr. Pompeo was scheduled to call Representative Devin Nunes of California, the top Republican on the Intelligence Committee, and a key ally of the president’s, just a few days after he spoke with Mr. Giuliani.

The emails do not have details of the telephone conversations.

But in an interview last month, Mr. Giuliani acknowledged that he spoke to Mr. Pompeo in late March — the same period as the calls listed in the emails released Friday — to relay information he had gathered during his Ukrainian research.

In connection with one such conversation, Mr. Giuliani said he provided Mr. Pompeo a timeline listing what he considered to be key events implicating targets of Mr. Trump, including the Bidens, Ms. Yovanovitch and Ukrainians whom Mr. Giuliani said had disseminated damaging information about Mr. Trump’s 2016 campaign chairman, Paul Manafort.

Shortly after, Mr. Pompeo “called and said, ‘Do you have any backup?’” Mr. Giuliani said in the interview.

In response, Mr. Giuliani said, he had someone hand-deliver to Mr. Pompeo’s office an envelope containing a series of memos detailing claims made by a pair of Ukrainian prosecutors in interviews conducted by Mr. Giuliani and his associates in January.

Mr. Pompeo “said he was referring it for investigation,” Mr. Giuliani said, adding that he had since heard that the matters detailed in the memos were referred to the State Department’s inspector general and the F.B.I.

Last month, the department’s inspector general turned over to congressional impeachment investigators a package of materials, including the memos and the timeline, in a Trump Hotel-branded envelope, prompting widespread puzzlement on Capitol Hill about its provenance.

The memos and the timeline were among the materials included in the document release on Friday.

Mr. Giuliani said the memos were written by a retired New York City police detective who works for Mr. Giuliani’s security consulting business and were modeled after the so-called 302 forms that F.B.I. agents file after conducting interviews.

“My guy ­— a former first-grade detective — wrote up what would be the 302,” Mr. Giuliani said. “They’re knockoffs of the 302s,” he added.

The memos include a mix of facts and unsubstantiated claims. They cite documents from Latvia and billing invoices. And they misspell the name of one of the Ukrainian prosecutors.

The memos indicate that the police detective was present for the interviews, as were Lev Parnas and Igor Fruman, Soviet-born associates who helped Mr. Giuliani connect to the prosecutors and gather information from Kyiv. Mr. Parnas and Mr. Fruman were indicted last month on campaign finance charges, in a case that is tied to an investigation into Mr. Giuliani for possible violations of lobbying laws.

Since at least spring 2018, Mr. Parnas and Mr. Fruman had pushed for Ms. Yovanovitch’s ouster.

The effort gained traction this spring when figures in the conservative news media claimed without evidence that Ms. Yovanovitch had privately disparaged Mr. Trump, and also cited the allegations by the Ukrainian prosecutors.

A letter to the State Department from two senior Democratic lawmakers in the House dated April 12 — just days before Ms. Yovanovitch was ordered to leave her post — said they were concerned by “outrageous efforts by Ukrainian officials to impugn” her. Ms. Yovanovitch, a career official, has served as an ambassador for Republican and Democratic presidents.

The reply from the agency, dated June 1, left the impression that Ms. Yovanovitch departed her post on May 20 because she had been scheduled to rotate out after three years, rather than indicating that she had been forced to leave.

The documents also include a letter dated April 5 from six former United States ambassadors to Ukraine to top State Department officials under Mr. Pompeo. In the letter, the former ambassadors said that they were “deeply concerned” about the charges against Ms. Yovanovitch that had emerged in the news media reports and that the accusations were “simply wrong.”

In late March, Ms. Yovanovitch told the third-ranking State Department official, David Hale, that she felt she could no longer continue in her role unless the department issued a statement in her defense. Mr. Hale briefed Mr. Pompeo about the conversation the next day, he testified to House investigators last week.

After looking into the right-wing campaign against Ms. Yovanovitch — even contacting Sean Hannity, the Fox News personality, to ask for details of wrongdoing — Mr. Pompeo believed that “there was no evidence” to support the allegations, Mr. Hale said in an earlier private testimony to lawmakers. But Mr. Pompeo ultimately chose not to issue a statement of support. (Mr. Hannity has denied any such call.)

John Sullivan, the deputy secretary of state, told senators last month that top State Department officials were aware of the smear campaign against Ms. Yovanovitch. Mr. Sullivan said he believed Mr. Giuliani was behind it.

In his retelling, Mr. Sullivan asked Mr. Pompeo why the president wanted to remove Ms. Yovanovitch. “I was told that he had lost confidence in her, period,” Mr. Sullivan said.

Representative Eliot Engel of New York, the chairman of the Foreign Affairs Committee and one of the lawmakers who sent the letter to Mr. Pompeo expressing concern over the smear campaign, said he initially found the department’s response “equally frustrating and baffling.”

“Now that we know more facts it makes sense: Secretary Pompeo was apparently helping the president with his scheme to get political help from the Ukrainians, and Ambassador Yovanovitch was standing in the way,” Mr. Engel said. “Six months later, Mr. Pompeo continues to defend the president’s behavior and defy congressional subpoenas for relevant information at the expense of the public servants he is unwilling to lead and defend.”

Mr. Pompeo has doubled down recently on his support of Mr. Trump’s demands on Ukraine. In several instances last month, Mr. Pompeo repeated an unsubstantiated claim by Mr. Trump — that Ukraine may have run an interference operation in the 2016 election. American intelligence officials and Fiona Hill, a Russia expert who served on Mr. Trump’s National Security Council, say that the falsehood has infected American discourse as part of a yearslong disinformation campaign by Russia.

Catie Edmondson contributed reporting.