Rechargeable lithium-ion polymer batteries have been considered to be next-generation power sources for portable electronic devices and electric vehicles. In this work, we tried to improve the cycling performances of lithium-ion polymer cells by coating aluminum fluoride and acrylonitrile-methyl methacrylate copolymer to the polyethylene separator. It was found that the addition of aluminum fluoride to the surface-modified separator reduced the interfacial resistances and thus the cell exhibited a less capacity fading and better high rate performance. The cell showed an initial discharge capacity of 150 mAh/g and good capacity retention at 0.5 C rate.