A novel approach for the surface modification of poly(vinylidene fluoride) (PVDF) membrane was successfully realized through alkaline treatment, UV-induced bromine addition, and followed by surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Chemical changes on the PVDF membrane before and after modification were analyzed with attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR) and X-ray photoelectron spectroscopy (XPS). Primary kinetic study revealed that the chain growth of poly(methyl methacrylate) (PMMA) from the PVDF surface is consistent with a “controlled” process.