Integration of organic and inorganic electronic materials is one of the emerging approaches to achieve novel material functionalities. Here, we demonstrate a stable self-assembled monolayer of an alkylsilane grown at the surface of graphite and graphene. Detailed characterization of the system using scanning probe microscopy, X-ray photoelectron spectroscopy, and transport measurements reveals the monolayer structure and its effect on the electronic properties of graphene. The monolayer induces a strong surface doping with a high density of mobile holes (n > 10(13) cm(-2)). The ability to tune electronic properties of graphene via stable molecular self-assembly, including selective doping of steps, edges, and other defects, may have important implications in future graphene electronics.