Celebrated fashion photographer Mario Testino shot the ad campaign with the Grey's Anatomy McDreamy, 41, last month, reports Access Hollywood.
"It was so lovely to work with Donatella Versace, she is an iconic and inspirational woman and a wonderful person, not to mention what a pleasure it was to work with Mario Testino too, one of the world's finest photographers," Dempsey said in a statement.
Said Versace of her new model: "I'm a big fan. So it was a great experience working with him because he is such a talented actor."
The ads will begin appearing in February, and StyleWatch readers, who got a heads-up last month, already marked their calendars.
Still SexyMeanwhile, when it comes to Dempsey's ranking in PEOPLE's Sexiest sweepstakes (behind Matt Damon this year, and George Clooney last), "He was robbed!" Amy Adams, his costar in the new movie hit Enchanted, insisted to the Associated Press. "That's what I think about that."
"That's funny," Dempsey said, laughing. "Always a bridesmaid, never a bride."