A polymer electrolyte based on poly(vinylidene) fluoride-hexafluoropropylene was prepared by evaporating the solvent of dimethyl formamide, and non-woven fabric was used to reinforce the mechanical strength of polymer electrolyte and maintain a good interfacial property between the polymer electrolyte and electrodes. Polymer lithium batteries were assembled by using LiCoO2 as cathode material and lithium foil as anode material. Scanning electron microscopy, alternating current impedance, linear sweep voltammetry and charge-discharge tests were used to study the properties of polymer membrane and polymer Li-ion batteries. The results show that the technics of preparing polymer electrolyte by directly evaporating solvent is simple. The polymer membrane has rich micro-porous structure on both sides and exhibits 280% uptake of electrolyte solution. The electrochemical stability window of this polymer electrolyte is about 5.5 V, and its ionic conductivity at room temperature reaches 0.151 S/m. The polymer lithium battery displays an initial discharge capacity of 138 mA·h/g and discharge plateau of about 3.9 V at 0.2 current rate. After 30 cycles, its loss of discharge capacity is only 2%. When the battery discharges at 0.5 current rate, the voltage plateau is still 3.7 V. The discharge capacities of 0.5 and 1.0 current rates are 96% and 93% of that of 0.1 current rate, respectively.