An issue with conventional vanadium redox flow batteries (VRFB) with Nafion membranes is the crossover of vanadium ions, resulting in low coulombic efficiency and rapid decay in capacity. In this work, a VRFB with a polybenzimidazole (PBI) membrane is tested and compared with the Nafion system. Results show that the PBI-based VRFB exhibits a substantially higher coulombic efficiency of up to 99% at current densities ranging from 20mAcm−2 to 80mAcm−2. More importantly, it is demonstrated that the PBI-based VRFB has a capacity decay rate of as low as 0.3% per cycle, which is four times lower than that of the Nafion system (1.3% per cycle). The improved coulombic efficiency and cycling performance are attributed to the low crossover of vanadium ions through the PBI membrane.