A new kind of alkoxy silane functionalized polymer (ASFP) is synthesized by selectively functionalized carboxyl groups as a novel inorganic precursor polymer to prepare organic-inorganic hybrid membrane for vanadium redox flow battery (VRFB) system. The novel hybrid membrane has been fabricated by interconnection between hydrophilic domains of Nafion and ASFP functional group. The effective concentration of ASFP for hybrid membrane is 25% (wt/wt). The proton conductivity and selectivity of the hybrid membrane are comparable with those of the Nafion212 membrane, which is mainly attributed by the presence of additional hydrophilic domains in the hybrid membrane. The proton conductivity and ion exchange capacity of the Nafion-ASFP (75:25) membrane is 0.061 S/cm and 0.68 meq/g, respectively. Remarkably, the Nafion-ASFP membrane shows a low vanadium permeability (1.259 x 10(-7) cm(2)/min) and high selectivity, which is an excellent advantage. As a result, the hybrid membrane shows comparable efficiency performance with Nafion212 over 50 cycles. Notably, the VRFB unit cell with Nafion-ASFP membrane achieves higher coulombic efficiency than Nafion212. The hybrid membrane reveals a new route to develop an alternative fluorinated polymer membrane with numerous advantages especially cost-effectiveness, homogeneous dispersion of inorganic silica precursor materials in the hybrid membrane without deterioration of mechanical strength, and lower vanadium ion crossover for VRFB system.