Single atom catalysts (SACs) with metal₁-N_x sites have shown promising activity and selectivity in direct catalytic oxidation of benzene to phenol. The reaction pathway is considered to be involving two steps, including a H₂O₂ molecule dissociated on the metal single site to form the (metal₁-N_x)=O active site, and followed by the dissociation of another H₂O₂ on the other side of metal atom to form O=(metal₁-N_x)=O intermediate center, which is active for the adsorption of benzene molecule via the formation of a C-O bond to form phenol. In this manuscript, we report a Cu SAC with nitrogen and oxygen dual-coordination (Cu₁-N₃O₁ moiety) that doesn’t need the first H₂O₂ activation process, as verified by both experimental and density function theory (DFT) calculations results. Compared with the counterpart nitrogen-coordinated Cu SAC (denoted as Cu₁/NC), Cu SAC with nitrogen and oxygen dual-coordination (denoted as Cu₁/NOC) exhibits 2.5 times higher turnover frequency (TOF) and 1.6 times higher utilization efficiency of H₂O₂. Particularly, the coordination number (CN) of Cu atom in Cu₁/NOC maintains four even after H₂O₂ treatment and reaction. Combining DFT calculations, the dynamic evolution of single atomic Cu with nitrogen and oxygen dual-coordination in hydroxylation of benzene is proposed. These findings provide an efficient route to improve the catalytic performance through regulating the coordination environments of SACs and demonstrate a new reaction mechanism in hydroxylation of benzene to phenol reaction.