Vanadium oxides are promising cathode materials for aqueous zinc-ion batteries due to their high theoretical capacity and multiple oxidation states but suffer from low conductivity and structural instability during cycling. We synthesized PEDOT-intercalated V2O5 via a simple one-pot route involving H2O2-assisted formation of layered structure followed by in-situ polymerization of EDOT at RT, 60, and 90 °C. Structural analysis confirmed PEDOT intercalation with interlayer expansion from 4.36 to 9.50 Å. XPS and FTIR showed that higher temperature promotes deeper intercalation and stronger electronic coupling with the oxide, while TEM directly revealed the redistribution of PEDOT from the surface into the bulk. Electrochemical tests revealed that the synthesis temperature determines the balance between capacity and stability. The 90 °C cathode delivered the highest capacity (434.9 mAh·g−1 at 1 A·g−1), while the RT sample showed superior stability (79% retention after 1000 cycles at 5 A·g−1). Surface-localized oligomers stabilize the structure, whereas deeply intercalated PEDOT enhances charge transfer. This work offers a scalable strategy for high-performance V2O5/PEDOT cathodes.