Graft copolymers of poly(vinylidene fluoride) with poly(methyl methacrylate) (PVDF-g-PMMA) and poly(oxyethylene methacrylate) (PVDF-g-POEM) were synthesized by the "grafting from" method, using polyvinylidene fluoride as macroinitiator for atom transfer radical polymerization (ATRP). The effects of polymerization temperature, reaction time and ATRP ligand were investigated. Products were characterized by gel-permeation chromatography (GPC), H-1-NMR, differential scanning calorimetry (DSC) and atomic force microscopy (AFM). Linear ln([M](0)/[M]) vs. time and molecular weight vs. conversion plots confirm the living nature of the graft copolymerization. AFM on PVDF-g-POEM revealed a microphase-separated morphology characteristic of graft copolymers.