Abstract The sorption of selenium(VI) onto pure anatase, a polymorph of titanium dioxide, was investigated. At the macroscopic level, batch experiments and electrophoretic mobility measurements were performed. Selenium(VI) retention was found to be pH-dependent, i.e. sorption of selenium(VI) decreases with increasing pH (pH range 3.5–11). Selenium(VI) sorption dependence on the ionic strength was also evidenced, i.e. sorption increases while the ionic strength decreases. Electrophoretic mobility measurements showed that selenium(VI) sorption had no effect on the isoelectric point of anatase. At the microscopic level, XPS (X-ray Photoelectron Spectroscopy) measurements evidenced the absence of reduction of selenium(VI) during the sorption process. Furthermore, the nature of the sorbed surface species at the anatase/liquid interface was elucidated using Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) spectroscopy. The spectroscopic results strongly suggested the formation of outer-sphere complexes on the whole pH range, in agreement with batch sorption experiments and electrophoretic mobility findings.