Electrospun poly(acrylonitrile) fibrous membrane (PAN-EFM) is prepared and enhanced by adding poly(methyl methacrylate)(PMMA) and subsequently minimizing the average diameter of the PAN/PMMA blend fibers. Electrospinning of the 50/50 wt% PAN/PMMA solution is carried out with the aim of the simultaneous presence of both polymers on the fiber surface. Their presence in exterior surface is confirmed using the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique next to the leaching of PMMA with acetone. The process parameters are optimized in four stable modes with the average diameter decreasing from 445 to 150 nm. Mechanical strength of the membrane is measured and reported. Comparing the sample electrochemical properties of the EFMs reveals that the addition of PMMA increases ionic conductivity from 1.02 to 3.31 mS cm(-1) and reduces interfacial resistance from similar to 1000 to similar to 400 a"broken vertical bar. It is also demonstrated that the similar to 300-nm reduction in average diameter of the blend fibers increases ionic conductivity from 3.31 to 5.81 mS cm(-1) and reduces interfacial resistance from similar to 400 to similar to 200 Omega.