The effects of Na2CO3 on the photocatalytic oxidation (PCO) of SO2 with UV irradiated TiO2 (P25) were studied using a fixed bed reactor. Na2CO3 was loaded onto P25 using a wet coating method. The PCO efficiency for SO2 with P25 was enhanced by 1.6 and 10.6 times using 0.05M and 0.2M Na2CO3 modified P25, respectively. The enhancement of the photocatalytic activity of P25 by Na2CO3 was observed only with the presence of water vapor. Low temperature (113 K) electron spinning resonance (ESR) analysis showed that Na2CO3 promoted the photoinduced electron-hole separation by trapping valance band holes and forming carbonate radicals (CO3 center dot-). The ESR spin trapping analyses showed a remarkable increase in the intensity of [DMPO-OH] adducts with the addition of Na2CO3. This increase phenomena indicates that more reactive species were formed on the P25 surface. The deposited Na2CO3 inhibited the recombination of electron-hole pairs and promoted the generation of hydroxyl radicals (center dot OH), most likely through the photo-reduction of O-2 adsorbed by the conduction band electrons. The generated center dot OH radicals reacted with SO2 rapidly and improved the PCO effectiveness of P25.