The Revlon chief served his fourth wife with divorce papers less than a month ago, the New York Post reported Friday.
A shoeless Barkin was seen directing "an army of burly movers" Thursday while complaining Perelman's armed security guards were hindering the operation, the newspaper said.
It was unclear where Barkin and her two children from her former marriage to actor Gabriel Byrne will now reside.
The Post said Barkin, 51, was blindsided by the divorce papers from Perelman, who now has to pay her $20 million under terms of a prenuptial agreement.
The couple met in 1999 and married in 2000.