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Grammer, 42, will team with the cable news network's Showbiz Tonight anchors AJ Hammer and Brooke Anderson to provide live red-carpet fashion commentary on Road Gold.
"We can't wait to get Camille's unabashed take on Hollywood's biggest night," said a CNN executive producer in a statement to PopEater.
Grammer's divorce to the Fraiser star was finalized on February 10. Kelsey Grammer plants to marry fiance Kayte Walsh, who is pregnant with his child.