Nanocrystalline rutile TiO2 powders were modified with small amounts of CuOx, and FeOx, clusters by impregnation and drying. The modified rutile samples exhibited drastically enhanced photocatalytic degradation of 4-chlorophenol under UV + vis (lambda > 320 nm) irradiation. The reaction rates were increased by the factor of 7 and 4 for the optimized TiO2(R)-CuOx, and TiO2(R)-FeOx, samples containing 0.12 wt.% Cu and 0.13 wt.% Fe, respectively. The visible light (lambda > 455 nm) activity in 4-CP degradation was negligible. Photopotential transient measurements have confirmed that amorphous CuOx, and FeOx, clusters deposited at the surface of rutile TiO2 act as efficient co-catalysts for oxygen reduction by photogenerated electrons, which leads to improved charge separation and diminished recombination. This study shows that simple modification of TiO2 photocatalysts with redox co-catalysts based on metal oxides is a promising strategy for enhancing the photocatalytic activity in degradation of aqueous pollutants. (c) 2013 Elsevier B.V. All rights reserved.