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Converting CO to useful compounds through the solar photocatalytic reduction has been one of the most promising strategies for artificial carbon recycling. The highly relevant photocatalytic substrate for CO conversion could be the popular TiO surfaces. However, the lack of accurate measurements for the energy level alignment that determines the CO reduction on TiO has limited our ability to control these complicated photocatalysis processes. We report here a systematic study on the reduction of CO at specific sites of the rutile TiO(110)- surface using scanning tunneling microscopy at 80 K. The dissociation of CO molecules is found to be activated by one electron attachment process with an energy threshold of 1.8 eV above the Fermi level (or 1.4 eV above the TiO conduction band onset), while the lowest unoccupied molecular orbital (LUMO) of the adsorbed CO is located at 2.3 eV with respect to the …