Highly porous free-standing co-poly(vinylidene fluoride)/modacrylic/SiO(2)nanofibrous membrane was developed using electrically-assisted solution blow spinning method. The performance and the potential of the membrane as a lithium-ion battery separator were investigated. The addition of modacrylic enhanced the solution spinnability that resulted in defect-free membranes. Moreover, the presence of modacrylic enhanced the dimensional and thermal stabilities, while the addition of hydrophilic SiO2 nanoparticle enhanced both mechanical property and ionic conductivity. Combustion test results illustrated that the presence of modacrylic provide flame retarding property over a set of different polymeric-based membranes. Electrochemical performance results showed that the developed membrane can increase the battery capacity compared with the commercial separator.