The formation of Ag nanoparticles on the surface of TiO2 (AgNP/TiO2) to enhance photocatalytic efficiency was studied. The Ag nanoparticles (AgNP) size, form, and distribution dependence on the initial thickness of Ag thin films, annealing temperature, and time were analyzed. The optimal annealing temperature of 400 °C and annealing time of 60 min were chosen to form AgNP from the initial Ag thin films with a thickness of 5, 7.5, and 10 nm. The formation of AgNP was done on amorphous TiO2 (a-TiO2), which crystallized into the anatase phase after the annealing. The photocatalytic efficiency (k–degradation rate constant, Defi–degradation efficiency) was evaluated by the photodegradation of Rhodamine B aqueous solution. The results suggested that the highest photocatalytic efficiency of Rhodamine B aqueous solution was reached where the average diameter (DA) of AgNP was ~38 nm (k38 = 0.017 min−1, Defi_38 = 63.5%), compared to 27 and 82 nm (k27 = 0.012 min−1, Defi_27 = 51.2% and k82 = 0.011 min−1, Defi_82 = 52.1%, respectively). The acquired results did not show clear correlation between the size and distribution of the AgNP on the TiO2 surface and photocatalytic efficiency. Nevertheless, the results suggest that AgNP can enhance the photocatalytic efficiency of TiO2 thin films (kTiO2 = 0.008 min−1, Defi_TiO2 = 36.3%).