Surface mesoscopic titanium dioxide (P25) films deposited onto conducting glass plates (SnO2:F) were modified by colloidal RuxSey nanoparticles (2 nm diameter). A decrease of the photocurrent was found upon modification of TiO2 films. However, interfacial electron transfer kinetics to oxygen was favored. The increase of the catalyst surface concentration onto TiO2, shifts the onset of the photocurrent under UV-illumination, to 0.6 V/RHE in presence of oxygen dissolved in the electrolyte. Concomitant to this, the cathodic current becomes important and shifts to more positive potentials. This phenomenon allows the system to work catalytically under open circuit conditions. On non-modified TiO2, the application of a 0.3 V/RHE potential leads to an enhancement of the photooxidation of formic acid. Photocurrent images revealed a non-homogeneous distribution of the catalyst on the titanium dioxide films. (C) 2004 Elsevier B.V. All rights reserved.