Metal-complex/semiconductor hybrids have attracted attention as photocatalysts for visible-light CO2 reduction, and electron transfer from the metal complex to the semiconductor is critically important to improve the performance. Here rutile TiO2 nanoparticles having 5-10 nm in size were employed as modifiers to improve interfacial charge transfer between semiconducting carbon nitride nanosheets (NS-C3N4) and a supramolecular Ru(II)-Re(I) binuclear complex (RuRe). The RuRe/TiO2/NS-C3N4 hybrid was capable of photocatalyzing CO2 reduction into CO with high selectivity under visible light (lambda > 400 nm), outperforming an analogue without TiO2 by a factor of 4, in terms of both CO formation rate and turnover number (TON). The enhanced photocatalytic activity was attributed primarily to prolonged lifetime of free and/or shallowly trapped electrons generated in TiO2/NS-C3N4 under visible-light irradiation, as revealed by transient absorption spectroscopy. Experimental results also indicated that the TiO2 modifier served as a good adsorption site for RuRe, which resulted in the suppression of undesirable desorption of the complex, thereby contributing to the improved photocatalytic performance. This study presents the first successful example of interfacial manipulation in a metal-complex/semiconductor hybrid photocatalyst for improved visible-light CO2 reduction to produce CO.