The targeted oxidization of trace NO to NO3- instead of toxic NO2via photocatalytic process represents one of the promising protocols for assuring environmental benefits. A novel type of graphite carbon nitride (CN) photocatalysts with high coordination sites (M–N5; M = Fe, Co, Mn, Ti) and far–carbon defects were manufactured by reconstructing the low coordination structure (M–N4). The mingled characterizations and theoretical calculations demonstrated that the reconstructed sites could improve the charge and energy transfer process of the exciton to precisely regulate the activation process of O2, while inhibiting the activation of adsorbed H2O. Superior orientation to form superoxide radical and singlet oxygen, rather than hydroxyl radical, showed excellent NO removal rates (68.6%) and superior NO3- selectivity (about 100%) under visible–light irradiation. This work proposes a unique mechanism via tailored construction of highly coordinated structures for selective NO oxidation to achieve the goal of atmospheric purification.