In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N-isopropylacrylamide) (PVDF-g-PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N-isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), H-1 NMR, gelpermeation chromatography (GPC), and X-ray photoelectron spectroscopy (XPS). The temperature-sensitive membrane was prepared from the PVDF-g-PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF-g-PNIPAAm membrane depended on the temperature change. (c) 2007 Wiley Periodicals, Inc.