"Today, there was a lot of soul-searching and discussion," a senior administration official told CNN regarding the resignations. "It was obviously the right thing to do."
In a letter to Trump announcing her resignation, DeVos said Trump's words served to encourage the rioters.
"There is no mistaking the impact your rhetoric had on the situation and it is the inflection point for me," she wrote.
Trump appeared at a rally in the Ellipse on Wednesday morning before his supporters, who had gathered outside the Capitol building as Congress met to certify President-elect Joe Biden's Electoral College win, made their way into the building.
Chao discussed the matter with her staff and her husband, Senate Republican leader Mitch McConnell, before deciding to resign, saying that Wednesday's riot was "entirely avoidable."
In a statement, Chao said the storm of the Capitol building "has troubled me in a way that I simply cannot set aside."
The decision of DeVos and Chao to resign could complicate calls for the Cabinet to invoke Section 4 of the 25th Amendment for the first time in history.
Later Thursday, Assistant Attorney General Eric Dreiband of the Justice Department's Civil Rights Division also resigned. In a statement, he said serving in the department "has been the honor of a lifetime."
Rep. Adam Kinzinger, R-Ill., became the first Republican to join House Speaker Nancy Pelosi, Senate Democratic leader Chuck Schumer and Democrats on the House Judiciary Committee in calling for the Cabinet to invoke the amendment, which states the president can be removed from power if the vice president and a majority of Cabinet members find him "unable to discharge the powers and duties of his office."