Pompeo acknowledged on Wednesday that he was on the telephone call between Donald Trump and his Ukrainian counterpart that sparked impeachment proceedings against the Republican president.
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.
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.