A CuGaO2 p-type semiconductor electrode was successfully employed for constructing a new hybrid photocathode with a Ru(ii)-Re(i) supramolecular photocatalyst (RuRe/CuGaO2). The RuRe/CuGaO2 photocathode displayed photoelectrochemical activity for the conversion of CO2 to CO in an aqueous electrolyte solution with a positive onset potential of +0.3 V vs. Ag/AgCl, which is 0.4 V more positive in comparison to a previously reported hybrid photocathode that used a NiO electrode instead of CuGaO2. A photoelectrochemical cell comprising this RuRe/CuGaO2 photocathode and a CoO x /TaON photoanode enabled the visible-light-driven catalytic reduction of CO2 using water as a reductant to give CO and O2 without applying any external bias. This is the first self-driven photoelectrochemical cell constructed with the molecular photocatalyst to achieve the reduction of CO2 by only using visible light as the energy source and water as a reductant.