Following a whistleblower complaint last week, Democrats are looking into Trump's request to Ukrainian President Volodymyr Zelenskiy during a July 25 phone call to investigate former Vice President Joe Biden.
Biden is a leading contender for the Democratic nomination to challenge Trump in the 2020 presidential election.
"I was on the phone call," Pompeo told reporters during a visit to Italy.
He said the call was in the context of U.S. policymaking in Ukraine, including "taking down the Russia threat," rooting out corruption in government and boosting the economy.
Trump made the request to Zelenskiy shortly after he had frozen nearly $400 million in U.S. aid to Ukraine. Democrats accuse Trump of soliciting foreign interference in a U.S. election and of using taxpayer money as leverage for personal political gain.
The call and the whistleblower's complaint prompted House of Representatives Speaker Nancy Pelosi to launch a formal impeachment inquiry on Sept. 24.
In an intensifying battle between Congress and the executive branch, lawmakers have subpoenaed Pompeo and Trump's personal lawyer Rudolph Giuliani, as well as documents. They will begin depositions of current and former State Department officials this week.
The department's inspector general, Steve Linick, was due to brief congressional staff on Wednesday to address Ukraine-related documents that have been subpoenaed, according to two sources familiar with the situation.
Pompeo on Tuesday objected to House efforts to obtain depositions and accused Democrats of bullying and intimidation.
Asked about his concerns, Pompeo said State Department employees had been contacted directly by lawmakers or their staff and told not to talk to the State Department's legal counsel.
He said, however, that he would cooperate with Congress.
"We will of course do our constitutional duty to cooperate with this co-equal branch but we are going to do so in a way that is consistent with the fundamental values of the American system," he said.
The heads of three House committees leading the impeachment probe have, in turn, accused Pompeo of intimidating witnesses, and said doing so was illegal.
The Democratic chairmen of the three committees warned Pompeo on Tuesday that he would be considered "a fact witness in the House impeachment inquiry" if he was on Trump's call with Zelenskiy.
TESTIMONY
Trump, who is seeking a second term in the election next year, has denied wrongdoing and assailed the impeachment probe.
According to a summary of the call released by the White House, Trump asked Zelenskiy during the July call to investigate Biden and his son Hunter in coordination with U.S. Attorney General William Barr and Giuliani.
Hunter Biden had sat on the board of a Ukrainian gas company that was under investigation by Kiev.
Kurt Volker, who resigned on Friday as Trump's special representative for Ukraine, was to go to Capitol Hill to give a deposition to House staff on Thursday, the day he had been asked to appear.
Marie Yovanovitch, who was U.S. ambassador to Ukraine until she was abruptly recalled in May, has agreed to appear on Oct. 11.
With their deep knowledge of Ukraine, testimony by Yovanovitch and Volker could be especially important to the impeachment probe.
The inquiry could lead to approval of articles of impeachment - or formal charges - against Trump in the House. That would lead to a trial in the Senate on whether to remove him from office. But the president's fellow Republicans control that chamber and have shown little appetite for removing him.