In an aqueous solution, photophysical, photochemical, and photocatalytic abilities of a Ru(II)Re(I) binuclear complex (RuReCl), of which Ru(II) photosensitizer and Re(I) catalyst units were connected with a bridging ligand, have been investigated in details. RuReCl could photocatalyze CO2 reduction using ascorbate as an electron donor, even in an aqueous solution. The main product of the photocatalytic reaction was formic acid in the aqueous solution; this is very different in product distribution from that in a dimethylformamide (DMF) and triethanolamine (TEOA) mixed solution in which the main product was CO. A (CO2)-C-13 labeling experiment clearly showed that formic acid was produced from CO2. The turnover number and selectivity of the formic acid production were 25 and 83%, respectively. The quantum yield of the formic acid formation was 0.2%, which was much lower, compared to that in the DMFTEOA mixed solution. Detail studies of the photochemical electron-transfer process showed back-electron transfer from the one-electron-reduced species (OERS) of the photosensitizer unit to an oxidized ascorbate efficiently proceeded, and this should be one of the main reasons why the photocatalytic efficiency was lower in the aqueous solution. In the aqueous solution, ligand substitution of the Ru(II) photosensitizer unit proceeded during the photocatalytic reaction, which was a main deactivation process of the photocatalytic reaction. The product of the ligand substitution was a Ru(II) bisdiimine complex or complexes with ascorbate as a ligand or ligands.