A novel molecular photocatalytic system with not only high reduction ability of CO2 but also high capture ability of CO2 has been developed using a Ru(II)-Re(I) dinuclear complex as a photocatalyst. By using this photocatalytic system, CO2 of 10% concentration could be selectively converted to CO with almost same photocatalysis to that under a pure CO2 atmosphere (TONCO > 1000, Phi(CO) > 0.4). Even 0.5% concentration of CO2 was reduced with 60% initial efficiency of CO formation by using the same system compared to that using pure CO2 (TONCO > 200). The Re(I) catalyst unit in the photocatalyst can efficiently capture CO2, which proceeds CO2 insertion to the Re-O bond, and then reduce the captured CO2 by using an electron supplied from the photochemically reduced Ru photosensitizer unit.