A novel Poly( phthalazinone ether sulfone ketone) (PPESK) membrane for lithium-ion battery was prepared using electrospinning technique. The morphology, electrochemical performances and thermal properties of electrospun PPESK fabrics were investigated. Results indicate that electrospun PPESK fabrics have high porosity of 92% and high electrolyte uptake of 1210%, which lead to their high ionic conductivity of 3.79 x 10(-3) S.cm(-1) at 25 degrees C. The cell assembled with PPESK fabrics displays better electrochemical stability and higher cycling discharge capacity than that assembled with PVDF fabrics. Moreover, electrospun PPESK fabrics exhibit excellent thermal dimensional stability. When PPESK fabrics are treated in oven at 220 degrees C for 1 h, the shape of membrane is unchanged. Electrospun PPESK fabrics have possible applications for high performance lithium-ion battery. (C) 2011 Elsevier B.V. All rights reserved.