Aqueous zinc-ion batteries is considered as a promising system for large scale electrochemical energy storage system owing to their intrinsic safety, and low cost. Nevertheless, the industrialization process is slow due to the constraints of high-performance cathode materials. Adjusting the layered structure of V2O5 through metal ion or polymer intercalation can effectively improve low electron conductivity, vanadium dissolution, and slow ion transport kinetics. Herein, the conductive polymer polypyrrole-intercalated V2O5·H2O (PVOH) was successfully prepared via simple hydrothermal method and following interface polymerization reaction. Getting benefit from the insertion of polypyrrole, the prepared PVOH composite material achieves a V2O5 cathode with a more open structure, rich active sites, and greater stability, allowing for an expanded crystal plane spacing of 14.5 Å. Therefore, the PVOH electrode demonstrates a discharge capacity of 475 mAh g−1 and a cycling stability of 95% capacity retention after 2000 cycles. The intercalating conductive polymers strategy can become a new approach to improve the electrochemical behavior of vanadium oxide cathodes.