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BiOCl photocatalysis shows great promise for molecular oxygen activation and NO oxidation, but its selective transformation of NO to immobilized nitrate without toxic NO2 emission is still a great challenge, because of uncontrollable reaction intermediates and pathways. In this study, we demonstrate that the introduction of triangle Cl−Ag1−Cl sites on a Cl‐terminated, (001) facet‐exposed BiOCl can selectively promote one‐electron activation of reactant molecular oxygen to intermediate superoxide radicals (⋅O2−), and also shift the adsorption configuration of product NO3− from the weak monodentate binding mode to a strong bidentate mode to avoid unfavorable photolysis. By simultaneously tuning intermediates and products, the Cl−Ag1−Cl‐landen BiOCl achieved >90 % NO conversion to favorable NO3− of high selectivity (>97 %) in 10 min under visible light, with the undesired NO2 concentration below 20 ppb. Both the activity and the selectivity of Cl−Ag1−Cl sites surpass those of BiOCl surface sites (38 % NO conversion, 67 % NO3− selectivity) or control O−Ag1−O sites on a benchmark photocatalyst P25 (67 % NO conversion and 87 % NO3− selectivity). This study develops new single‐atom sites for the performance enhancement of semiconductor photocatalysts, and also provides a facile pathway to manipulate the reactive oxygen species production for efficient pollutant removal. [ABSTRACT FROM AUTHOR]