A series of highly branched sulfonated poly (fluorenyl ether ketone sulfone)s (HSPAEK) are synthesized by direct polycondensation reactions. The HSPAEK with 8% degree of branching is further investigated as membrane for vanadium redox flow battery (VRFB). The HSPAEK membrane prepared by solution casting method exhibits smooth, dense and tough morphology. It possesses very low VO2+ permeability and high ion selectivity compared to those of Nafion 117 membrane. When applied to VRFB, this novel membrane shows higher coulombic efficiency (CE, 99%) and energy efficiency (EE, 84%) than Nafion 117 membrane (CE, 92% and EE, 78%) at current density of 80 mA cm−2. Besides, the HSPAEK membrane shows super stable CE and EE as well as excellent discharge capacity retention (83%) during 100 cycles life test. After being soaked in 1.5 mol L−1 VO2 + solution for 21 days, the weight loss of HSPAEK membrane and the amount of VO2+ reduced from VO2 + are only 0.26% and 0.7%, respectively, indicating the superior chemical stability of the membrane.