The Material Girl poses as a French bar girl in the saucy images, which show her posing seductively in just fishnet tights and stilettos, with the fashion giant's iconic handbag slung over her shoulder.
The pictures, which reportedly netted the star $9.85 million (£6.45million), were shot by Steven Meisel, the top snapper, who masterminded the controversial images released in her 1992 Sex book.
Madonna follows in the footsteps of Jennifer Lopez, Scarlett Johansson, and Uma Thurman as the latest face to promote the French fashion house.