Vanadium flow battery (VFB) shows great potential in balancing the volatility of renewable energy. In this work, we investigated, for the first time, the various properties of crystalline ZSM-5 membranes prepared through the organic template-free gel strategy in VFB. The subnano windows (∼0.55 nm) of ZSM-5 zeolite provided selective transport paths for protons (∼0.27 nm) and blocked the vanadium (>0.6 nm) migration through pore repulsion effect. The zeolite membranes exhibited a very low vanadium penetration rate (0.05 mmol L −1 h −1 ), achieving a Coulombic efficiency (CE) of 96.1%, a voltage efficiency of 78.3%, and an energy efficiency of 75.3% at the current density of 40 mA cm −2 . Notably, ZSM-5 prepared using the template-free strategy eliminates the need for a high-temperature calcination step, and the membrane has a lower defect density and exhibits a higher CE. The self-discharge time of the ZSM-5 zeolite membrane increased up to 78 h. Furthermore, the charge−discharge performance kept stable more than 300 cycles at 60 mA cm −2 .