The California-born model, who is 37 years old, was the face of the make-up brand in the early 1990s and helped launch its "Maybe she's born with it, maybe it's Maybelline" strapline in 1991.
Founded in the US in 1913, Maybelline was bought by L'Oreal in 1996, and was launched in the UK as Maybelline New York in 1998.
Other celebrities who have promoted the brand include Patsy Kensit, Eva Herzigova, Linda Evangelista, Kate Moss and Elle MacPherson.
Cheryl Vitali, senior vice-president for marketing at Maybelline New York-Garnier, said: "Christy is a perfect match for Maybelline New York -- she is a natural beauty and exudes confidence. We are thrilled to have Christy rejoin the Maybelline New York family."
After leaving the catwalk in 1994, Turlington completed a degree in religion and philosophy at New York University, going on to create her own yoga and fashion clothing brands Nuala and Mahanuala with sportswear company Puma.
Turlington said: "It is definitely exciting to return with a whole new variety of life experiences that I can share with a new audience of women."
A global TV campaign, created by Interpublic-owned New York agency Gotham, will begin at the end of August with print following in September.
If you have an opinion on this or any other issue raised on Brand Republic, join the debate in the Forum.