The White House staff secretary said “these outrageous allegations are simply false” as he announced he would step down.
The accusations were first reported in the Daily Mail and include accounts of physical and emotional abuse.
The White House would not comment on a report that Rob Porter, 40, failed to receive security clearance.
His ex-wives, Colbie Holderness and Jennifer Willoughby, both recounted stories of Rob Porter’s alleged misconduct.
Colbie Holderness, the first wife and a government analyst, said the White House aide had been verbally and physically abusive.
She said Rob Porter had kicked her on their 2003 honeymoon in the Canary Islands.
Colbie Holderness also alleged he punched her in the face while they were on holiday a couple of years later in Florence, Italy.
She supplied a photo of herself with a black eye to the media.
The second wife, Jennifer Willoughby, a motivational speaker, told the Daily Mail she was married to Rob Porter from 2009 to 2013.
She wrote about her experiences in a blog post entitled Why I Stayed.
Jennifer Willoughby said she filed a protective order against him in June 2010 after he allegedly punched the glass of the door at their Alexandria, Virginia, home.
She told the Washington Post on February 7: “He has never faced repercussions that forced him to confront his issues.
“I care about him and want what’s best for him, but that doesn’t necessarily mean him keeping his job because he needs to face these underlying issues.”
Rob Porter rejected the allegations in a statement read by the White House press secretary on February 7.
“I took the photos given to the media nearly 15 years ago and the reality behind them is nowhere close to what is being described,” he said.
“I have been transparent and truthful about these vile claims, but I will not further engage publicly with a co-ordinated smear campaign.”
According to the Daily Mail, RobPorter did not receive security clearance for his White House job after the FBI interviewed his ex-wives during background checks.
However, the White House press secretary Sarah Huckabee Sanders refused to be drawn on that issue.
She told reporters: “Background checks involve a complex investigation run by intelligence and law enforcement agencies.
“As has always been our policy, we do not comment on security clearances. Rob Porter has been effective in his role as Staff Secretary.
“The President and Chief of Staff have full confidence in his abilities and his performance.”
Rob Porter attended Harvard with Jared Kushner, the president’s son-in-law, and was a Rhodes Scholar at Oxford University.
His White House role involved working with the president and his chief of staff John Kelly.
Before Rob Porter resigned, John Kelly told the Daily Mail the staff secretary was “a man of true integrity and honor”.
According to the reports, Rob Porter has recently been romantically linked with White House communications director Hope Hicks.
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