Hydrophilic poly(vinylidene fluoride) (PVDF) porous membranes are facilely fabricated via grafting polymerization and cross-linking reaction for vanadium flow battery (VFB) application. A solvent swelling pre-treatment is specifically carried out to introduce hydrophilic groups in the pores and on the surface, where they can form well connected ion transport networks. The modification is performed through chemical cross-linking and grafting of PVP by using potassium persulfate (K2S2O8) as a radical initiator. The effect of reaction condition on membrane morphology, hydrophilicity is characterized in detail. Meanwhile, the performance of modified membranes is detected in VFB single cell at a current density of 80 mA cm−2. It is found that more PVP is immobilized on membrane surface and in the pores with prolonging reaction time. Consequently, the membrane wetability and effective pore size change dramatically, resulting better hydrophilicity and higher ion selectivity. As a result, the VFBs assembled with these modified membranes show higher CE and overall better EE than unmodified ones. The optimized membrane shows CE of 94.4% and EE of 83.3%, which is comparable to commercial Nafion 115. Furthermore, the prepared hydrophilic PVDF membranes demonstrate excellent chemical stability through the long-term battery operation, showing great prospects in VFB applications.