A supercritical carbon dioxide(Sc CO2) assisted phase inversion was developed to produce microporous poly(vinylidene fluoride)(PVDF) membranes whose morphology characteristics arise from both liquid-liquid demixing and solid-liquid demixing(crystallization). This result was confirmed by Fourier transform infrared spectroscopy(FTIR), from which both α and β crystals were found. As revealed by contact angle experiment, the PVDF membranes prepared via Sc CO2 assisted phase inversion were more hydrophobic compared with the control membrane produced via conventional immersionprecipitation technique. In particular, the sample with 15 wt% PVDF prepared at 45 °C and 13 MPa exhibited a contact angle of 142°, which was mainly caused by the multilevel micro- and nano- structure. The effects of polyethylene glycol(PEG), polyvinyl pyrrolidone(PVP) and lithium chloride(Li Cl) on the structures and crystal form were investigated. PVP promoted the formation of β phase crystal form, while PEG boosts the evolution of α phase. Li Cl restrained the crystallization degree of PVDF membrane under Sc CO2. A supercritical carbon dioxide (ScCO) assisted phase inversion was developed to produce microporous poly (vinylidene fluoride) (PVDF) membranes whose morphology characteristics arise from both liquid-liquid demixing and solid-liquid demixing (crystallization). This result was confirmed by Fourier As described by contact angle experiment, the PVDF membranes prepared via ScCO 2 assisted phase inversion were more hydrophobic compared with the control membrane produced via conventional immersion precipitation technique. , the sample with 15 wt% PVDF prepared at 45 ° C and 13 MPa was a contact angle of 142 °, which was mainly caused by the multilevel micro- and nano- structure. The effects of polyethylene glycol (PEG), polyvinyl pyrrolidone ( PVP) and lithium chloride (LiCl) on the structures and crystal forms were investigated. PVP promoted the formation of β phase crystal form, while PEG boos ts the evolution of α phase. Li Cl restrained the crystallization degree of PVDF membrane under Sc CO2.