Oxidative coupling of CO is a straightforward and economic benign synthetic route for value-addedα-diketone moiety containing C2or higher carbon compounds in both laboratory and industry, but is still undeveloped to date. In this work, a rare coplanar dinuclear hydroxycarbonylcobalt(III) complex, bearing a Schiff-base macrocyclic equatorial ligand and aμ-κ1(O):κ1(O’)-acetate bridging axial ligand, is synthesized and characterized. The Co(III)-COOH bonds in this complex can be feasibly photocleaved, leading to the formation of oxalic acid. Moreover, the light-promoted catalytic direct production of oxalic acid from CO and H2O using O2as the oxidant with good selectivity (> 95%) and atom economy at ambient temperature and gas pressure based on this dicobalt(III) complex have been achieved, with a turnover number of 38.5. The13C-labelling and18O-labelling experiments confirm that CO and H2O act as the sources of the -COOH groups in the dinuclear hydroxycarbonylcobalt(III) complex and the oxalic acid product.