There has been increasing interest in artificial photosynthetic schemes for converting the greenhouse gas, carbon dioxide, into a value added fuel such as methanol. Although photoelectrochemical schemes, utilizing a semiconductor-electrolyte interface that is responsive to sunlight have been considered for this application, all reports to date indicate that excessive overpotentials are required, and thus, photoelectrochemical cells have not been observed to actually convert light energy to chemical energy in CO2 reduction systems. However, we have developed a catalytic system that efficiently and selectively converts carbon dioxide to methanol and other multi-carbon organics. The system couples either a semiconductor or metal electrode with a substituted pyridinium catalyst. In certain cases, we find that the reaction can be driven solely with visible or near UV light to yield faradaic efficiencies approaching 100% at potentials well below the thermodynamic potential required in the absence of light. In addition to methanol and related C1 products, both higher order alcohols and aldehydes can be photochemically synthesized appropriately coupling a pyridinium electrocatalyst with an electrode interface.