David Sorensen denies his former wife's allegations he was violent and emotionally abusive.
His departure comes just days after another Trump official, Rob Porter, quit over allegations of abuse from two ex-wives, something he denies.
Questions have been raised over how long it took the White House to act on the accusations facing Mr Porter.
What are the latest allegations?
Mr Sorensen's ex-wife Jessica Corbett told the Washington Post that he was physically abusive to her while they were married.
She said that on separate occasions her former husband ran a car over her foot, threw her against a wall and extinguished a cigarette on her hand.
In response, Mr Sorensen released a statement in which he said he had "never committed violence of any kind against any woman in my entire life" and that instead it was he who had been physically abused.
He said he was considering legal action, but said he quit because he "didn't want the White House to have to deal with this distraction".
White House officials said they learned of the accusations by Mr Sorensen's wife late on Thursday.
"We immediately confronted the staffer, he denied the allegations and he resigned today," deputy press secretary Raj Shah said.
What happened with Mr Porter?
Allegations of domestic abuse against Mr Porter involving two ex-wives surfaced on Tuesday.
It is alleged that the former White House staff secretary gave one ex-wife a black eye while another filed a restraining order. He denies both.
On Friday, Mr Trump paid tribute to Mr Porter, who quit his White House position on Wednesday.
Speaking in the Oval Office Mr Trump said: "We found out about it recently and I was surprised by it, but we certainly wish him well and it's a tough time for him."
But Mr Trump did not refer to Mr Porter's accusers.
His comments sparked criticism from Democrats, with former Vice-President Joe Biden saying Mr Trump had downplayed the allegations against Mr Porter.
"That's like saying: 'That axe murderer out there, he's a great painter'", Mr Biden said.
What's the fallout been?
The case has put pressure on Mr Trump's Chief-of-Staff John Kelly, who has denied reports he offered to resign over his handling of the accusations.
After initially praising Mr Porter as a man of "integrity", Mr Kelly later released a statement saying he was shocked by the claims and stressed domestic violence was unacceptable.
US media report that Mr Kelly and other White House officials were aware for several months of the domestic abuse accusations because they were holding up Mr Porter's security clearance application.
Mr Shah said that Mr Trump was not aware of any security issues before Tuesday and was "disheartened" and "saddened" by the accusations.
White House communications director Hope Hicks' handling of the controversy has also reportedly displeased Mr Trump.
The 29-year-old aide has recently been in a relationship with Mr Porter, a Harvard graduate and former Oxford Rhodes Scholar.
Mr Trump was reportedly not consulted when Ms Hicks helped draft an initial statement defending Mr Porter.
Who knew what and when?
According to CBS News, Mr Porter approached White House Counsel Don McGahn in January 2017 to inform him his ex-wives might say unflattering things about him to background check investigators.
In June 2017, Mr Porter's preliminary file was sent from the FBI to the White House security office, containing the abuse allegations.
In November, Mr McGahn received a call from an ex-girlfriend of Mr Porter alleging physical violence by the aide.
Mr McGahn told the White House chief of staff there was an issue with Mr Porter's security clearance, although he was vague, reports CBS.
Mr Porter told Mr Kelly his ex-wives were saying false things about him.
A White House spokesman said on Thursday that Mr Kelly did not realise the extent of the claims until a photo of one of Mr Porter's former wives, Colbie Holderness, suffering a black eye, emerged on Wednesday.
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