The photocatalytic performance of anatase TiO2 nanorod-stabilized Ag nanoparticles has been investigated during the reductive bleaching of a model dye, Uniblue A (UBA), in homogeneous organic solutions. The activity of the TiO2/Ag nanocomposite has been found to vary continuously during the course of photocatalysis, following a concomitant light-induced modification of the metal nanoparticle size and size distribution. The direct involvement of the metal particles in mediating electron transfer between photoexcited TiO2 and the target UBA is explained on the basis of the size-dependent redox properties of the metal nanoparticles. The present results can be useful in the design of new composite materials with well-tailored photocatalytic properties and long-term stability.