Commercial TiO2 samples with different phase composition and surface area were tested as photocatalysts in the photoinduced reduction of Cr(VI) in aqueous suspensions at pH 3.7 under UV-visible light irradiation. This reaction was also coupled with the simultaneous photocatalytic oxidation of the pollutant azo dye Acid Orange 8 (AO8) and of formic acid, acting as hole scavengers. The co-presence of oxidizable and reducible species ensured better separation of photogenerated charge carriers, resulting in a higher rate of both organics' oxidation and Cr(VI) reduction, especially in the case of high surface area anatase TiO2, having the strongest affinity for Cr(VI) and AO8, as demonstrated by competitive adsorption tests. The effects on Cr(VI) photocatalytic reduction of gold nanoparticles photodeposited on TiO2 and of the Au loading were also investigated, aiming at ascertaining if this noble metal plays a role in the electron transfer processes involved in Cr(VI) reduction. (c) 2011 Elsevier B.V. All rights reserved.