Abstract: Using perfluorinated sulfonic acid (PFSA) as the main polymer and hydrophobic polymer polyvinylidene fluoride (PVDF) as addictive, PFSA-PVDF composited nanofiber membranes were prepared by the electrospinning method. Various characterization methods such as conductivity, viscosity, surface tension, dynamic light scattering, scanning electron microscope and differential scanning calorimeter were conducted to study the effect of PFSA-PVDF mass ratios on solution property, morphology and physical property. Results showed that the strong interaction between PVDF and PFSA leaded to an increase in the viscosity of the mixed solution, and effectively improved the solution electrospinnability. The fiber diameter distribution became uniform with the increase of PVDF content.