A solvent responsive sol–gel method is adopted to fabricate poly (ether sulfone) (PES)/silica composite porous membranes for vanadium flow battery (VFB) application. The pore size and pore size distribution of the composite membrane can be easily adjusted by controlling the quantity of silica gels inside the pores of pristine membranes. Fourier transform infrared spectroscopy (FT-IR) and energy dispersive spectrometer (EDS) are carried out to confirm the structure of resulted membranes. VFBs assembled with the silica modified membranes display much higher coulomb efficiency (97%) and energy efficiency (83%) than that of pristine porous membrane (CE 86%, EE 76%). Furthermore，the modified PES membranes demonstrate high oxidation stability through the long-term battery operation. The PES/silica composite porous membranes show great prospects in VFB applications.