A ternary plasmonic photocatalyst consisting of Au-decorated V2O5@ZnO heteronanorods was successfully fabricated by an innovative four-step process: thermal evaporation of ZnO powders, CVD of intermediate on ZnO, solution deposition of Au NPs, and final thermal oxidization. SEM, TEM, EDX, XPS, and XRD analyses revealed that the interior cores and exterior shells of the as-prepared heteronanorods were single-crystal wurtzite-type ZnO and polycrystalline orthorhombic V2O5, respectively, with a large quantity of Au NPs inlaid in the V2O5 shell. The optical properties of the ternary photocatalyst were investigated in detail and compared with those of bare ZnO and V2O5@ZnO. UV-vis absorption spectra of ZnO, V2O5@ZnO, and Au-decorated V2O5@ZnO showed gradually enhanced absorption in the visible region. In addition, gradually decreased emission intensity was also observed in the photoluminescence (PL) spectra, revealing enhanced charge separation efficiency. Because of these excellent qualities, the photocatalytic behavior of the ternary photocatalyst was studied in the photodegradation of methylene blue under UV-vis irradiation, which showed an enhanced photodegradation rate nearly 7 times higher than that of bare ZnO and nearly 3 times higher than that of V2O5@ZnO, mainly owing to the enlarged light absorption region, the effective electron-hole separation at the V2O5-ZnO and V2O5-Au interfaces, and strong localization of plasmonic near-field effects.