In this study, the short-and long-range chem-ical environments of Cu dopant in TiO 2 photocatalyst have been investigated. The Cu-doped and undoped TiO 2 spec-imens were prepared by the sol–gel approach employing CuSO 4 Á5H 2 O and Ti(O-iPr) 4 precursors and subjecting the dried gels to thermal treatment at 400 and 500 °C. The photocatalytic activity, investigated by methylene blue degradation under sunlight irradiation, showed a signifi-cantly higher efficiency of Cu-doped samples than that of pure TiO 2 . The X-ray diffraction results showed the pres-ence of anatase phase for samples prepared at 400 and 500 °C. No crystalline CuSO 4 phase was detected below 500 °C. It was also found that doping decreases the crys-tallite size in the (004) and (101) directions. Infrared spectroscopy results indicated that the chemical environ-ment of sulfate changes as a function of thermal treatment, and UV–vis spectra showed that the band gap decreases with thermal treatment and Cu doping, showing the lowest value for the 400 °C sample. X-ray absorption fine struc-ture measurements and analysis refinements revealed that even after thermal treatment and photocatalytic assays, the Cu 2? local order is similar to that of CuSO 4 , containing, however, oxygen vacancies. X-ray photoelectron spec-troscopy data, limited to the near surface region of the catalyst, evidenced, besides CuSO 4 , the presence of Cu 1? and CuO phases, indicating the active role of Cu in the TiO 2 lattice.