Abstract Conventional vanadium redox flow batteries (VRFBs) using Nafion 115 suffered from issues associated with high ohmic resistance and high capital cost. In this work, we report a commercial membrane (VANADion), consisting of a porous layer and a dense Nafion layer, as a promising alternative to Nafion 115. In the dual-layer structure, the porous layer (∼210 μm) can offer a high ionic conductivity and the dense Nafion layer (∼20 μm) can depress the convective flow of electrolyte through the membrane. By comparing with the conventional Nafion 115 in a VRFB, it is found that the change from the conventional Nafion 115 to the composite one results in an increase in the energy efficiency from 71.3% to 76.2% and an increase in the electrolyte utilization from 54.1% to 68.4% at a current density of as high as 240 mA cm−2. In addition, although two batteries show the comparable cycling performance at current densities ranging from 80 mA cm−2 to 240 mA cm−2, the composite membrane is estimated to be significantly cheaper than the conventional Nafion 115 due to the fact that the porous layer is rather cost-effective and the dense Nafion layer is rather thin. The impressive combination of desirable performance and low cost makes this composite membrane highly promising in the VRFB applications.