The 33-year-old model sits on a red inflatable toy for her cover wearing nothing but high heels and her long hair in lose waves.
Last month Barbadian singer Rihanna, 26, made headlines for appearing topless on the cover of the glossy. At the time, the singer engaged in a dispute with image sharing site Instagram after the site reportedly warned her to tone down the nudity of her posts if she wanted to keep her account.
Bundchen's cover for Lui comes days after it was revealed that she'd become the new face of Chanel's fragrance Chanel No. 5. The Brazilian beauty also covers the June issue of Vogue Brasil along soccer star Neymar.
2014: The Year in Fashion [PHOTOS]
Polly Bergen, Emmy Award-winning actress, dies