A bifunctional supramolecular complex Ru(phen)2(phen-cyclam-Ni)(ClO4)4 (6) (phen-cyclam = 1-(1,10-phenanthrolin-5-ylmethyl)-1,4,8,11-tetraazacyclotetradecane) has been newly synthesized, and its spectroscopic, redox properties, and catalytic behavior in the photoreduction Of CO2 have been examined. The new binuclear complex 6 is shown to be an interesting hybrid molecule composed of a Ru(phen)3(2+) (phen = 1,10-phenanthroline) subunit, which acts as a photosensitizer, and a Ni(cyclam)2+ catalytic reduction site.