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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 V 2 O 5 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 V 2 O 5 ·H 2 O (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 V 2 O 5 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. [Display omitted] • The conductive polymer polypyrrole-intercalated PVOH was successfully prepared. • The PVOH has a more open structure, rich active sites, and an expanded crystal plane spacing of 14.5 Å. • The PVOH electrode demonstrates a discharge capacity of 475 mAh g−1 at 0.1 A g−1. • A detailed investigation is conducted on the co-insertion mechanism of Zn2+/H+ by the different ex-situ characterization. [ABSTRACT FROM AUTHOR]