A photocatalytic strategy has been developed to synthesize colloidal Ag-TiO2 nanorod composites in which each TiO2 nanorod contains a single Ag nanoparticle on its surface. In this rational synthesis, photoexcitation of TiO2 nanorods under UV illumination produces electrons that reduce Ag(I) precursor and deposit multiple small Ag nanoparticles on the surface of TiO2 nanorods. Prolonged UV irradiation induces an interesting ripening process, which dissolves the smaller nanoparticles by photogenerated oxidative species and then redeposits Ag onto one larger and more stable particle attached to each TiO2 nanorod through the reduction of photoexcited electrons. The size of the Ag nanoparticles can be precisely controlled by varying the irradiation time and the amount of alcohol additive. The Ag-TiO2 nanorod composites were used as electron transport layers in the fabrication of organic solar cells and showed notable enhancement in power conversion efficiency (6.92%) than pure TiO2 nanorods (5.81%), as well as higher external quantum efficiency due to improved charge separation and transfer by the presence of Ag nanoparticles.