Iron-mediated atom transfer radical polymerization using activators generated by electron transfer directly from the secondary fluorine atoms on the poly(vinylidene fluoride) (PVDF) backbone, using methyl methacrylate (MMA) and poly (ethylene glycol) methyl ether methacrylate (PEGMA) as the monomers, FeCl(3 center dot)6H(2)O as the catalyst, PPh(3) as the ligand, and vitamin C as the reducing agent, was demonstrated in the presence of limited amounts of air. The successful syntheses of the corresponding graft copolymers PVDF-g-PMMA and PVDF-g-PPEGMA were characterized by nuclear magnetic resonance, Fourier transform infrared and X-ray photoelectron spectroscopy, respectively. The graft copolymers PVDF-g-PPEGMA can be readily cast into porous hydrophilic microfiltration membranes by phase inversion in an aqueous medium. The morphologies were characterized by scanning electron microscopy. The surface and bulk hydrophilicity were evaluated on the basis of static water contact angle and the steady adsorption of bovine serum albumin. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2315-2324, 2011