Abstract: The ZrO₂/PVDF-PAN composite membranes based as poly(vinylidene fluoride) (PVDF) and polyacrylonitrile(PAN) with different ZrO₂ contents were prepared by electrospinning. The morphology and specific surface area were characterized by SEM and BET, respectively. The results show that the morphologies of the composite membranes depend on the ZrO₂ content. With the increasing of ZrO₂ content, the surface of fibers becomes unsmooth and the specific surface area and liquid absorption rate increase, and they reach the maximum when the ZrO₂ content is 0.4% of the mass of PVDF and PAN. To study the effect of ZrO₂ content on electrochemical performance of composite membranes, super-capacitors were fabricated with the composite membrane as separators. Test results of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show that composite membrane with 0.4wt% ZrO₂ possesses excellent electrochemical performance, in which the specific capacitance value and ionic conductivity reach 126.0 F/g and 9.31×10^-3 S/cm, respectively.