Grafting of polymer brushes on the poly(vinylidene fluoride) (PVDF) films was carried out by the surface-initiated free radical polymerization. Surface-initiators were immobilized on the PVDF films by surface hydroxylation and esterification of the surface-tethered hydroxyl groups with 4,4'-azobis(4-cyanopentanoic acid) (ACP). Homopolymer brushes of methyl methacrylate (MMA) were prepared by free radical polymerization from the azofunctionalized PVDF surface. The chemical composition and topography of the graft-functionalized PVDF surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FTIR spectroscopy, and atomic force microscopy (AFM). Kinetics study revealed an exponential increase in the graft concentration of polymer brushes with the reaction time, indicating that the chain growth from the surface was consistence with a chain polymerization. Water contact angles on PVDF films were reduced by surface grafting of MMA. (c) 2006 Wiley Periodicals, Inc.