To develop a novel and low-cost membrane as a separator of vanadium redox flow battery, sulfonated poly(phthalazinone ether sulfone) (SPPES) was prepared by sulfonating PPES with fuming sulfuric acid. By testing the sulfonation degree, intrinsic viscosity, and solubility of SPPES, the results showed that sulfonated polymers had higher intrinsic viscosities and excellent solubility in most polar solvents. IR analysis revealed that the –SO3H group was successfully attached to SPPES backbone. DSC and TG results showed that SPPES exhibited higher T g than that of PPES, and T d at the first weight loss of SPPES was about 300 °C. The SPPES membrane (SP-02) showed a dramatic reduction in crossover of vanadium ions across the membrane compared with that of the Nafion membrane. Cell tests identified that VRB with the SPPES membrane exhibited a lower self-discharge rate, higher coulombic efficiency (92.82%), and higher energy efficiency (67.58%) compared with the Nafion system. Furthermore, cycling tests indicated that the single cell with SPPES membrane exhibited a stable performance during 100 cycles.