In this study, TiO2 photoanodes doped with samarium ions via a method of hydrothermal treatment were used to fabricate dye-sensitized solar cells (DSSCs). Different doping concentrations were investigated on the effects of the cell’s performance. Some techniques including XRD, scanning electron microscopy, HRTEM, XPS, UV-Vis, photoluminescence were used to characterize the morphology, structure, and optic properties of the prepared photoanodes. The photovoltaic performance of the fabricated cells was further evaluated by measuring the current density–voltage (J–V) curves. It was found that: (1) The down-conversion luminescence effect derived from samarium doping could enhance the light-harvesting ability. (2) Compared with the undoped sample, the samarium-doped cells exhibited enhanced photovoltaic performance. Among the cells with different doping concentrations, the cell TiO2:0.015 Sm showed the best power conversion efficiency of 6.08% with a high open-circuit voltage (V
oc) and a short-circuit current density (J
sc).