The treatment of nitrate (NO3−) pollutants is crucial for human health in the context of environmental pollution. Synergistic photocatalytic redox technology is feasible for reducing low-concentrated NO3− to achieve environmental purification. As combined redox reactions proceed in one photocatalysis system, incorporating suitable oxidative reactions is one potential strategy to enhance photocatalytic NO3− reduction efficiency. Herein, almost 100 % removal efficiency of NO3− and superior N2 selectivity of 93.99±0.45 % is achieved through the precise matching of synergistic oxidative half-reactions. The crucial role of active radicals is revealed. Specifically, the conversion efficiency of NO3− is determined by the cooperation of formate radicals (•CO2−), which are generated from the selective oxidation of formaldehyde, acetaldehyde or glyoxal. Among them, the optimum yield of •CO2− radicals are reached from the formaldehyde oxidative reaction. It is clarified that this research will contribute to a deep understanding of the removal and purification of NO3− in wastewater.