Thursday's ruling upholds a lower court decision.
The actress and Perelman divorced in 2006. During the marriage, the couple and Barkin's brother George launched Applehead Pictures.
Perelman acknowledges he didn't pay more than $3.4 million he'd agreed to put into the venture. He says the Barkins negated his obligation by forming another film company, among other actions.
The state Supreme Court's Appellate Division says Perelman still must pay.
The Barkin camp's lawyer says he hopes the decision ends the matter.
Perelman's lawyers and spokeswoman didn't immediately respond to telephone and e-mail messages.