The 33-year-old, who divorced Tom Cruise recently, is set to front Brown's iconic makeup brand, which launched in 1991, reported Us magazine.
Holmes is busy planning for her upcoming New York Fashion Week debut, in which she will show her new line on the same day as singer-fashion designer Victoria Beckham.
The actress is also set to head back to Broadway this fall for the first time since in 2008, when she performed in 'All My Sons'.