Photochemical reduction involves chemical reduction (redox) generated from the photoexcitation of another molecule, called a photosensitizer. To harness the sun's energy, the photosensitizer must be able to absorb light within the visible and ultraviolet spectrum. 
Molecular sensitizers that meet this criterion often include a metal center, as the d-orbital splitting in organometallic species often falls within the energy range of far-UV and visible light. The reduction process begins with excitation of the photosensitizer, as mentioned. This causes the movement of an electron from the metal center into the functional ligands. This movement is termed a metal-to-ligand charge transfer (MLCT). Back-electron transfer from the ligands to the metal after the charge transfer, which yields no net result, is prevented by including an electron-donating species in solution. Successful photosensitizers have a long-lived excited state, usually due to the interconversion from singlet to triplet states, that allow time for electron donors to interact with the metal center.
Common donors in photochemical reduction include triethylamine (TEA), triethanolamine (TEOA), and 1-benzyl-1,4-dihydronicotinamide (BNAH).
After excitation, CO coordinates or otherwise interacts with the inner coordination sphere of the reduced metal. Common products include formic acid, carbon monoxide, and methanol. Note that light absorption and catalytic reduction may occur at the same metal center or on different metal centers. That is, a photosensitizer and catalyst may be tethered through an organic linkage that provides for electronic communication between the species. In this case, the two metal centers form a bimetallic supramolecular complex. And, the excited electron that had resided on the functional ligands of photosensitizer passes through the ancillary ligands to the catalytic center, which becomes a one-electron reduced (OER) species. The advantage of dividing the two processes among different centers is in the ability to tune each center for a particular task, whether through selecting different metals or ligands.