White House staff secretary Rob Porter 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 Mr Porter, 40, failed to receive security clearance.
His ex-wives, Colbie Holderness and Jennifer Willoughby, both recounted stories of Mr Porter's alleged misconduct.
His first spouse, Ms Holderness, said the White House aide had been verbally and physically abusive.
Ms Holderness, a US government analyst, said Mr Porter had kicked her on their 2003 honeymoon in the Canary Islands.
She also alleged he punched her in the face while they were on holiday a couple of years later in Florence, Italy.
Ms Holderness supplied a photo of herself with a black eye to the media.
Ms Willoughby, a motivational speaker, told the Daily Mail she was married to Mr Porter from 2009-13.
She wrote about her experiences in a blog post entitled Why I Stayed.