The remarkable limitations in photocatalysis still remain: low utilization of visible light, poor charge transfer and separation, and insufficient active sites. To address these issues, herein, Au-Bi2WO6 hybrid photocatalysts are synthesized through a one-step solvothermal method, possessing a good combination of plasmonic Au nanoparticles (NPs) and abundant oxygen vacancies (OVs) in the hybrid nanostructures. The Au-Bi2WO6 hybrid photocatalyst with an optimal Au content exhibits outstanding activity and selectivity toward selective oxidation of aromatic amines under visible light, far outperforming pure Bi2WO6 nanostructures. The collaborative contributions of hot charge carriers from Au NPs, photoexcited electron-hole pairs from Bi2WO6, and the OVs for efficient adsorption-activation of molecular O-2 result in the enhanced photocatalysis for selective oxidation under visible-light irradiation. This study will motivate the rational construction of metal semiconductor hybrid photocatalysts with multiple active sites and boost the utilization of solar energy to drive a broad range of organic transformations.