We tested 4.2 V Li-ion polymer batteries (LIPB) with physical gel electrolyte, poly(vinylidene fluoride) (PVDF), 4.4 V LIPB and 4.4 V Li-ion batteries (LIB) with a liquid electrolyte. The discharge capacity of the 4.4 V LIPB reached 520 Wh l -1 which was 9% higher than that of the 4.2 V LIPB. The 4.4 V LIPB had a high capacity retention ratio of 91.4% at 3 C because of the excellent ion conductivity of the PVDF gel. The capacity retention ratio of the 4.4 V LIPB was 82% after 500 cycles, which is comparable to those of some commercial LIBs. The 4.4 V LIPB retained its original thickness even after many cycles and after being stored at 90 °C, whereas the 4.4 V LIB swelled by over 20%. Peaks in the FT-IR spectrum of the discolored separator in the 4.4 V LIB after storage were assigned to C dbnd C double bonds, suggesting that the separator in direct contact with the 4.4 V cathode had been oxidized. The PVDF gel electrolyte not only had a high ionic conductivity but also completely suppressed oxidation. The 4.4 V LIPB with PVDF gel electrolyte has properties suitable for practical cells, namely, high energy density, high permanence and it is safe to use.