The simultaneous photocatalytic degradation of phenol and 4-nitrophenol and reduction of metal ions like copper (Cu2+) and chromium (Cr 6+) was studied with solution combustion synthesized nanoanatase TiO2 (CS TiO2) and commercial titania, Degussa P-25. The presence of metal ion reduces the rate of degradation of phenol and 4-nitrophenol. It was found that Cu2+ reduction to Cu+ is accelerated in the presence of phenol. In the case of Cr6+, CS TiO2 enhances the initial adsorption of Cr6+ and complete reduction is achieved within the first 10 min of UV irradiation. The presence of phenol or 4-nitrophenol also enhances the initial adsorption of Cr6+ and its reduction. The metal ion reduction in the presence of CS TiO 2 is compared with that of Degussa P-25. The rate of reduction of metal ions in presence of Degussa P-25 is twice as slow as that of CS TiO 2 in presence of both phenol and 4-nitrophenol. The presence of Cu2+ and Cr6+ also induces the formation of the intermediates which were not observed forthe phenol-CS TiO2 system. The formation and consumption of the intermediates are modeled with a simple series reaction mechanism. A detailed dual-cycle, multistep reaction mechanism of TiO2 photocatalysis for the simultaneous degradation and reduction is proposed and the model is developed following the network reduction technique. The kinetic rate constants in the model are evaluated for the systems studied. © 2008 American Chemical Society.