PVDF membrane formation via TIPS was performed for PVDF/DBP and PVDF/DMP systems. PVDF/DBP system showed solid-liquid phase separation behavior, while PVDF/DMP system has liquid-liquid phase separation characteristic as well as solid-liquid phase separation characteristic. PVDF contents and cooling conditions had great influence on structure, and the effects of each parameter were examined. Spherulitic structure was obtained due to the dominant PVDF crystallization. Diluent rejected to the outside of spherulite occupied the surface of the PVDF spherulites to result in the microporous spherulite formation and micro-void between spherulites. PVDF/DMP system had competitive solid-liquid and liquid-liquid phase separation depending on the cooling path.