Molinaro was appointed along with Barry Schwartz, executive vice chairman at MacAndrews and Forbes Holdings Inc., to serve on the CUNY Board of Trustees.
"[They] will bring invaluable experience from both the public and private sectors to the university," Cuomo said in a statement.
"I thank them for their leadership as CUNY continues to serve the students of New York City with the highest standards.”
Molinaro will leave the office after three-terms in January, being replace by borough president-elect James Oddo.
Molinaro and Schwartz will replace Kathleen Pesile and Jeffrey Wiesenfeld, whose tenure on the board expired, Cuomo said.