When hexavalent chromium (Cr(VI)) is added to a TiO2 photocatalytic reaction, the decolorization and mineralization efficiencies of azo dyes Acid Orange 7 (AO7) are enhanced even though the mechanism is unclear. This study used 5,5-dimethyl-L-pyrroline-N-oxide (DMPO) as the scavenger and the analysis of Electron Spin Resonance (ESR) to investigate this enhancement effect by observing the hydroxyl radical ((OH)-O-center dot) generation of the Cr(VI)/TiO2 system under UV and visible light (Vis) irradiation. With Cr(VI), the decolorization efficiencies were approximately 95% and 62% under UV and Vis, and those efficiencies were 25% less in the absence of Cr(VI). The phenomena of the DMPO-OH signals during the ESR analysis under Vis 405 and 550 nm irradiation were obviously the enhancement effects of Cr(VI) in aerobic conditions. In anoxic conditions, the catalytic effects of Cr(VI) could not be achieved due to the lack of a redox reaction between Cr(VI) and the adsorbed oxygen at the oxygen vacancy sites on the TiO2 surfaces. The results suggest that by introducing the agents of redox reactions such as chromate ions, we could lower the photoenergy of TiO2 needed and allow Vis irradiation to activate photocatalysis. (C) 2014 Elsevier B.V. All rights reserved.