Polyoxometallates (POMs) have been attracting much attention as homogeneous molecular catalysts because of their excellent photocatalytic activities. However, the poor sensitivities of POMs to visible light limit their utilization of solar energy. Here, we studied photoinduced electron transfer (PET) from a Ru complex to POMs such as SiW10O368-, W10O324-, SiW12O404-, and PMo12O403- to use them for photoenergy storage and photocatalysis driven by visible light. A hydrophobic Ru complex ([Ru(nbpy)3]2+ nbpy = 4,4′-dinoyl-2,2′-bipyridyl) was coupled with POMs that were hybridized with dioctadecyldimethylammonium (DODA) in chloroform. Photoluminescence (PL) quenching and lifetime measurements indicate that PET efficiently occurred from the Ru complex to the POMs/DODA hybrids in chloroform by excitation with visible light. The PET led to the formation of one-electron reduced POMs that store photoexcited electrons. The stored/charged electrons can be discharged in a subsequent reaction that can proceed under dark conditions. The Ru complex-POM hybrid system in chloroform was used to reduce metal ions in a water phase at a liquid/liquid interface under visible light irradiation. The one-electron reduced POM that was formed by PET could reduce metal ions to produce metal particles, suggesting the applicability of this system for photocatalytic reactions under visible light irradiation.