Highly porous poly(vinylidene-hexafluoropropylene) (PVdF-HFP) membranes were prepared by electrospinning with and without coconut shell flour (CSF) for the first time. The membranes were subjected to scanning electron microscopy (SEM), thermogravimmetric (TG), tensile, ionic conductivity and compatibility analyses. The 2032-type coin cells composed of Li/polymer membrane (PM)/LiMn1/3Ni1/3Co1/3O2 were assembled and their cycling profile was analyzed at 1 C rate. The incorporation of high surface area CSF on the nanofibres has significantly increased the mechanical integrity, electrolyte retention and ionic conductivity. The discharge capacity of the cell with CSF-added electrospun polymeric membrane was found to be higher than that of the commercially available Celgard separator.