The performance of UV/TiO2 (100 mg/L TiO2) process for Orange II degrdation was emphatically compared at pH 2.3, 6.9 and 11.5 by means of UV-Visible spectra, ionic chromatography, TOC, and HPLC analyses. The results revealed that the reaction intermediates were produced in different contents with the increasing reaction time due to the different pH conditions. The dye was oxidized more completely at pH 2.3 while the highest color removal percentage was achieved at pH 11.5. It was proved that active electrons, which is photo-generated along with positive holes on TiO2, not only contribute to the discoloration and mineralization of the dye due to the producing of oxidative species such as O2•- and •OOH, but also contribute to the discoloration of Orange II as reductive species. The most possible mechanism was put forward to explain the key roles of active electrons in dye degradation by UV/TiO2 process at pH 2.3 and 11.5.