The Localized Surface Plasmon (LSP) effect of 5 nm mean size Au particles deposited on TiO2 P25 was investigated during the photo-thermal water gas shift reaction (WGSR). The effects of CO concentration, excitation light flux and energy, and molecular oxygen addition during the reaction were investigated. The photocatalytic WGSR rate under light excitation with wavelengths extending from 320 to 1100 nm was found to be higher than the thermal reaction alone at the same temperature (85 °C). A H2/CO2 ratio of near unity was found at high concentrations of CO. The addition of molecular oxygen during the reaction resulted in a slight decrease in molecular hydrogen production, while the rates of CO2 formation and CO consumption changed by one order of magnitude. More importantly, it was found that the WGSR rates were still high under only visible light excitation (600–700 nm). The results prove that Au LSP alone triggers this chemical reaction without requiring the excitation of the semiconductor on which they are deposited