Morphologically controlled indium oxide nanocubes were synthesized, contacted with pure anatase nanoparticles, and used in the dual photothermocatalytic valorization of carbon dioxide. The series of samples with an indium oxide loading up to 20 wt % were subjected to a detailed physicochemical analysis. The catalysts synthesized are high surface area mesoporous materials. Interface effects coming from the contact between the two oxide components were analyzed and found to control the charge carrier recombination taking place under illumination. The catalytic activity under dual photothermo conditions showed optimum profit of the combination of the two energy sources with a sample having a 10 wt % of indium oxide. This sample shows a synergistic use of the dual excitation with an excess of ca. 50% as measured by the reaction rate. This excess appears at the top of the literature. The synergy observed would be linked with the optoelectronic effects controlled by the oxide−oxide interface.