Later, when introducing the best foreign language film, she had a poke at host Ricky Gervais (who joked she remains "just like a virgin").
"If I'm still just like a virgin, Ricky. Then why don't you come over here and do something about it," she said with a smile. "I haven't kissed a girl in a few years. On TV."
Madonna's "Masterpiece" is a moody ballad featuring a simplified production reminiscent of her sound in the 1990s, while the lyrics lean on the emotional side and tie into the film's love story. It was co-written by James Harry.
Starring James D'Arcy and Andrea Riseborough as King Edward VIII and his lover Wallis Simpson, "W.E." tells the story of when the monarch abdicated his throne in 1936 to marry the twice-divorced American.
The song was not short-listed for the best original song Oscar and reviews for the film have been mixed.
In the original score category, Frenchman Ludovic Bource ("The Artist") bested Trent Reznor and Atticus Ross, who were angling to repeat last year's win, for "The Social Network," with David Fincher's "The Girl With the Dragon Tattoo."
For full coverage of the 69th Golden Globe Awards go here.