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Ion exchange membranes play a key role in all vanadium redox flow batteries (VRFBs). The mostly available commercial membrane for VRFBs is Nafion. However, its disadvantages, such as high cost and severe vanadium‐ion permeation, become obstacles for large‐scale energy storage. It is thus crucial to develop an efficient membrane with low permeability of vanadium ions and low cost to promote commercial applications of VRFBs. In this study, graphene oxide (GO) has been employed as an additive to the Nafion 212 matrix and a composite membrane named rN212/GO obtained. The thickness of rN212/GO has been reduced to only 41 μm (compared with 50 μm Nafion 212), which indicates directly lower cost. Meanwhile, rN212/GO shows lower permeability of vanadium ions and area‐specific resistance compared to the Nafion 212 membrane due to the abundant oxygen‐containing functional groups of GO additives. The VRFB cells with the rN212/GO membrane show higher Coulombic efficiencies and lower capacity decay than those of VRFB cells with the Nafion 212 membrane. Therefore, the cost‐effective rN212/GO composite membrane is a promising alternative to suppress migration of vanadium ions across the membrane to set up VRFB cells with better performances.

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