Rechargeable Li battery cells were fabricated using a composite of crystalline V2O5 and polypyrrole (V2O5/PPy) as the positive electrode material and a gel electrolyte film based on cross-linked poly(methylmethacrylate) (PMMA). The pure polypyrrole electrode and the conventional V2O5 electrode (V2O5/C), the latter of which was a mixture of V2O5, acetylene black, and Teflon(R) binder, were also used for comparison. The PMMA gel electrolyte, showing no liquid leakage even under pressure, was prepared when the amount of the electrolyte solution in the polymer gel was reduced to 65 wt %. The V2O5/PPy electrode in the battery cell showed a capacity density that was 98.4% of its capacity density obtained in the electrolyte solution. Repeat of charge-discharge tests caused capacity fading when the V2O5/C and the V2O5/PPy composite containing 91wt % oxide were used. However, no change in the capacity density was observed up to 50 cycles for the composite electrodes containing 84 and 60 wt % oxide and the pure polypyrrole electrode. AC impedance measurements were conducted by using a three-electrode system to obtain the interfacial properties between the positive electrode and the gel electrolyte. It was found that the interfacial resistance was largely increased by charge-discharge cycling when the electrodes showing definite capacity fading were used, but the stable electrodes did not show such behavior.