In this study, various commercialized ion conductive membrane were analyzed by chemico-physical degradation. Chemico-physical degradation of Dupont’s Nafion 212 as a reference material, and F. Co. Ltd.’s cation exchange membrane F-1, anion exchange membrane F-2, and F-3 was analyzed to confirm the characteristics suitable for VRFB’s operation. To study ion exchange membrane’s degradation mechanism, experiments regarding hydrolytic stability, permeability and chemical stability of VO₂⁺ ion were also conducted. In order to compare the performance of VRFB’s long term operation, the membrane’s chemical stability was tested. After hydrolytic stability test, it was confirmed that there was a decrease in polymer’s weight and in distilled water’s pH, which leads to membranes’ degradation. To test the stability of polymer membrane and degradation mechanism, it was soaked in 0.1 M V(V) solution for 72 h. Then, change in concentration was measured by UV-vis Spectrum. Stability of F-series membrane showed higher stability than Nafion membrane, indicating a suitable membrane for VRFB’s long-term operation.