Polyoxometalates (POMs) as a homogeneous photocatalyst and semiconductor oxide as a heterogeneous photocatalyst share many aspects of similarity in their operating mechanisms. This study systematically compares various photocatalytic oxidation and reduction reactions of PW12O403- (a POM) and TiO2 in water to demonstrate that the two photocatalysts are very different in many ways. Both POM and TiO2 can photooxidize various organic compounds with comparable rates, but the POM-mediated mineralization is markedly slower than the mineralization with TiO2 under the experimental conditions employed in this study. Kinetic studies using tert-butyl alcohol as an OH radical scavenger suggest that OH radicals are the sole dominant photooxidant in POM-mediated degradations regardless of the kind of substrates tested, whereas both OH radicals and direct hole transfers take part in TiO2 photocatalysis. POM immobilization on silica support and surface fluorination of TiO2 significantly modified the kinetics and intermediate distribution. POM-mediated photoreductive dechlorination of CCl4 and trichloroacetate was negligible, whereas the dechlorination with TiO2 was markedly faster. The rate of electron transfer from POM-to reducible substrates seems to be significantly slower than the rate of conduction band electron transfer on TiO2 mainly due to the strong electron affinity of POM. The effects of H2O2 addition on photocatalytic reactivity are also very different between POM and TiO2. Detailed kinetic and mechanistic comparisons between PW12O403- and TiO2 photocatalysts are presented and discussed to understand the similarities and differences.