The photocatalytic degradation of 4-chlorophenol in water using Ru-doped ZnO mixed oxides (0, 0.5, 1, and 3 wt% RuO 2 ) synthesized by the one-pot homogeneous coprecipitation method is reported. ZnO with wurtzite structure was present in the mixed oxide as corroborated by Raman spectroscopy and X-ray diffraction analysis. All the samples showed nanorod morphological features. The presence of Ru 6+ /Ru 4+ couples on ZnO modified the band gap of the mixed oxides and led to a shift of the band gap energy from 3.20 eV to 3.07 eV. Ru addition increased the surface area and significantly promoted the formation of active surface oxygen species such as hydroradicals evidenced by the fluorescence spectroscopy measurement. In the photodegradation of 4-chlorophenol solution under UV irradiation, a notable increase in photoactivity was obtained as the amount of RuO 2 in the mixed oxides increased to 3 wt%. The charge transfer between Ru 6+ /Ru 4+ couples and ZnO nanoparticles together with the formation of free radical oxidant species effectively inhibits electron-hole recombination rate, thus favoring the photodegradation of 4-chlorophenol.