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A hetero-nanostructured photoanode with enhanced near-infrared light harvesting is developed for photo-electrochemical cells. By spatially coating upconversion nanoparticles and quantum dot photosensitizers onto TiO2 inverse opal, this architecture allows direct irradiation of upconversion nanoparticles to emit visible light that excites quantum dots for charge separation. Electrons are injected into TiO2 with minimal carrier losses due to continuous electron conducting interface.