For rare-earth doped semiconductors, charge propagation from semiconductors to rare-earths is essential for excitation of optically active dopants. However, the qualitative model that has been widely accepted to describe this process is based upon indirect evidence; in this model, it is believed that trapping and subsequent recombination of the charges at some rare-earth-related defect excite the dopants. In this work, we observe the sequential process directly, and quantify the trapped charge density and relaxation frequency using a photoelectric measurement technique for samarium-doped titanium dioxide with intense visible luminescence under ultraviolet light.