Highly flexible, paper-like, free-standing V2O5 and V2O5–polypyrrole (PPy) films were prepared via the vacuum filtration method. The films are soft, lightweight, and mechanically robust. The electrochemical performance of the free-standing pure V2O5 electrode was improved by incorporating conducting polypyrrole. A bendable cell with a novel design was fabricated, consisting of a free-standing V2O5–PPy cathode film, gel electrolyte, and a lithium foil anode. The cell was tested under repeated bending conditions for several cycles. The results show that the battery performance of the repeatedly bent cell was similar to that of the conventional cell.