A novel sandwich-type sulfonated poly(ether ether ketone) (SPEEK)/tungstophosphoric acid (TPA)/polypropylene (PP) composite membrane for a vanadium redox flow battery (VRB) has been developed with improved properties: the permeability of vanadium ions is greatly reduced and the performance of the VRB cell is greatly increased. The membrane is based on a traditional SPEEK membrane embedded with TPA but PP is used to enhance the membrane for the first time. Although its voltage efficiency (VE) is a little lower than that of a Nafion 212 membrane, it is expected to have good prospects for VRB systems because of its low cost and good performance.