House Democrats on Tuesday evening made good on their threat to subpoena a State Department witness they say has “deeply relevant” documents to the impeachment inquiry.

The chairmen of three House committees subpoenaed Gordon Sondland, the ambassador to the European Union. He was expected to testify before Congress on Tuesday morning before President Trump and Secretary of State Mike Pompeo intervened to block his testimony.

“Secretary Pompeo’s obstruction of the House’s impeachment inquiry does not alleviate you of your independent legal obligation to produce to the committees any responsive documents in your personal possession, custody or control,” the chairmen of the Intelligence, Foreign Affairs and Oversight and Reform committees wrote.

The subpoena demands Mr. Sondland testify before the committees on October 16 and provide documents by October 14.

Earlier Tuesday, House Intelligence Committee Chairman Rep. Adam Schiff said the State Department was withholding materials on a personal device that Mr. Sondland turned over.

“It is hard to overstate the significance of not just Ambassador Sondland’s testimony and documents but the testimony of others as well. The failure to produce this witness, the failure to produce these documents, we consider yet additional strong evidence of obstruction of the constitutional functions of Congress, a co-equal branch of government,” Mr. Schiff said.

The fight marks the first test for Democrats as they seek to compel witness testimony about whether President Trump sought to withhold military aid in exchange for Ukraine leaders investigating political rival Joseph R. Biden.

Democrats have repeatedly threatened to bring obstruction of justice as an impeachment article if the White House blocks key testimony.

The White House’s decision to block Mr. Sondland’s testimony came only hours before he was set to appear.

Republicans say Democrats are running an “unfair process,” saying Kurt Volker, the former U.S. envoy to Ukraine who testified last week, was treated poorly.

“That treatment is the reason why the administration and the State Department said we are not going to subject Ambassador Sondland to the same treatment,” said Rep. Jim Jordan, Ohio Republican.

In a pair of tweets, Mr. Trump said he would “love” to have Mr. Sondland testify, but doesn’t trust Democrats to give him a fair shake.

“Would love to send Ambassador Sondland, a really good man and a great American, to testify, but unfortunately he would be testifying before a totally compromised kangaroo court, where Republican’s rights have been taken away, and true facts are not allowed out for public to see,” the president tweeted.

Mr. Trump also chided the media, saying they failed to report on a Tweet sent earlier this week from Mr. Sondland. In the tweet, Mr. Sondland said Democrats were “incorrect” about the president’s intentions.

“The president has been crystal clear: no quid pro qous of any kind,” Mr. Sondland tweeted.

Robert Luskin, the attorney representing Mr. Sondland, said in a statement that as a State Department employee, his client had to comply with the administration’s directive.

“Ambassador Sondland is profoundly disappointed that he will not be able to testify today,” Mr. Luskin said. “Ambassador Sondland believes strongly that he acted at all times in the best interests of the United States and he stands ready to answer the committee’s questions fully and truthfully.”

Mr. Trump directed the ambassador to take the lead in building the relationship between Ukraine and the United States. In that capacity, Mr. Sondland reported directly to the president.

Text messages turned over to Congress last week revealed that Mr. Sondland and another official wrote a statement they wanted Ukraine president Volodymyr Zelensky to release that would have committed to an investigation of Mr. Biden and the Ukrainian business dealings of his son, Hunter.

Both diplomats discussed the statement with Rudolph W. Giluliani, the president’s personal attorney.

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