Bismuth‐based photocatalysts have been widely employed in the photocatalytic degradation of organic pollutants in wastewater. However, the lack of rational structural design and the slow generation of active free radicals have hindered its efficiency. Here, we stabilized Bi2WO6 nanoparticles by wrapping them with hydroxyl groups, introduced metal Cu doping, and underwent an annealing process to construct Cu‐BiNP nanocatalysts with exposed active sites. Under visible light irradiation, 0.03Cu‐BiNP achieved a 94.5% TC degradation efficiency, which is 15.8 times higher than the rate of bulk BiWO. The 0D structure endows Cu‐BiNP with ample opportunities for O2 adsorption and activation, and Cu atomic doping reduces the bandgap and increases the oxygen vacancy, promoting the generation of active oxygen species. This work demonstrates the rapid charge separation and activation of O2 to generate active oxygen species by 0D bismuth‐based nanocatalysts in photocatalytic oxidation reactions, providing a scalable nanocatalyst platform for TC photocatalytic degradation.