A novel Polyethylene oxide/lignocellulose (PEO/LIGC) coated dimpled electrospun P(VDF-TrFE) nanofibrous membranes were prepared and are employed as a separator for lithium-ion battery. ESEM images revealed the dimpled morphology of electrospun fibers and PEO/LIGC is located on the surface as well as in the space between the fibers. Results of tensile studies prove that PEO/LIGC coating improves the mechanical strength and elongation at break. The wettability of the membrane with liquid electrolyte was studied by contact angle analysis and the results indicate that both the membranes are readily wetted by the electrolyte. The electrolyte uptake of ecofriendly LIGC coated sample is ∼ 440%, which is 647% higher than that of commercial Celgard separator. PEO/LIGC coated membrane shows ∼ 86% porosity, which is 226% higher than that of the Celgard separator. Ionic conductivity studies show that dip coated P(VDF-TrFE) exhibits a conductivity 7. 04 × 10−3 S cm−1. A 2320 type coin cell (Li/Separator/LiFePO4) were fabricated using PEO/LIGC coated P(VDF-TrFE) and the fabricated cell is superior to that of a Celgard 2320 separator. Thus, the study reveals that the lignocellulose, a sustainable material helps to enhance the overall performance of the battery.