The novel supramolecular complexes, which are composed of an [Os(5dmb)2(BL)](2+)-type complex (5dmb = 5,5'-dimethyl-2,2'-bipyridine; BL = 1,2-bis(4'-methyl-[2,2'-bipyridin]-4-yl)ethane) as a photosensitizer and cis,trans-[Re(BL)(CO)2{P(p-X-C6H4)3}2](+)-type complexes (X = F, Cl) as a catalyst, have been synthesized. They photocatalyzed selective reduction of CO2 to CO under red-light irradiation (λ > 620 nm). The photocatalytic abilities were affected by the phosphine ligands on the Re unit, and the supramolecule with P(p-Cl-C6H4)3 ligands exhibited better photocatalysis (ΦCO = 0.12, TONCO = 1138, TOFCO = 3.3 min(-1)). The detailed studies clarified the electron balance and material balance; i.e., one molecule of the sacrificial electron donor (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH)) donated two electrons, one molecule of CO2 accepted the two electrons, and another CO2 molecule served as an "O(2-)" acceptor to give each molecule of the two-electron oxidized compound of BIH, CO, and HCO3(-).