Abstract: A type of graphene-modified polyvinylidene fluoride (PVDF) membranes were fabricated by supercritical CO2-induced phase separation using DMF as a solvent, and their morphology, thermal stability, thermodynamic properties, crystal transformation and hydrophilicity were studied. The results indicated that the microporous membranes obtained a good network structure at a low content of graphene under the process conditions of 8 MPa and 45 ℃. The pore size and roughness of the membranes were found to decrease, and however their hydrophilicity and thermal stability were improved. In addition, the introduction of graphene had little effect on thermodynamic properties but enhanced the transition of crystal form to form more β or γ crystals.