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[Display omitted] The introduction of oxygen-defects has been a versatile strategy to enhance photocatalysis efficiency. In this work, a 2D/3D Bi/BiO 2-x /Bi 2 WO 6 heterojunction photocatalyst with rich oxygen-defective was in sequence prepared through a facile solvothermal method, which displays favorable photocatalytic activity towards organic contaminants under visible-NIR light irradiation. The enhancement in photocatalytic performance can be attributed to the synergistic effect between oxygen-vacancy-rich heterojunction and the localized surface plasmon resonance induced by metallic Bi. The functional group interaction, surface morphology, crystal structure, element composition, and tuned bandgap were investigated by FT-IR, SEM, Raman shift, ICP-MS, and XPS technique. The spectrum response performance of the photocatalyst was verified by UV–visible DRS analysis. Results of photodegradation experiments toward organic contaminants showed that the prepared photocatalyst can degrade 90% of phenol in 20 mins under visible-NIR light irradiation, both Z-scheme heterojunction and the introduction of Bi metal contribute to the enhancement in the photocatalytic activity. The results of the DFT calculation suggest that the valence band-edge hybridization within BiO 2-x and Bi 2 WO 6 can effectively enhance the photocatalytic performance by increasing the migration efficiencies of electron-hole pairs. Moreover, a possible mechanism was proposed on the results of EIS, ESR and GC–MS tests. This work offers a novel insight for synthesizing efficient visible-NIR light photocatalysis by activating the semiconductors with Bi metal. [ABSTRACT FROM AUTHOR]