Porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) membranes were successfully prepared using dibutyl phthalate (DBP), polyvinylpyrrolidone (PVP-K30), polyethylene glycol 200 (PEG200) as templates. SEM was used to examine the morphology of the PVDF-HFP porous membranes. It was found that these membranes have an asymmetric structure and the blends of PVDF-HFP/DBP formed nanoporous membranes, whereas the blends of PVDF-HFP/PVP-K30 formed "sponge-like" and microporous membranes. Moreover, the average pore size and porosity was about 0.3 μm and 48.7%, respectively. The crystallinity, thermal stability and mechanical strength of membranes were characterized by XRD, DSC, TGA and stress-strain tests. The results showed that the membranes are α crystals with excellent thermal stability. It was an effective way to regulate pore size and morphology of the PVDF-HFP membranes.