In this study, we explore the effects on the incorporation of europium (Eu3+) and terbium (Tb3+) rare-earth ions into titanium dioxide (TiO2) photoanodes in dye-sensitized solar cells (DSSCs). X-ray photoelectron spectroscopy (XPS) studies affirm that the Eu3+ ions are arranged at the cationic locales of Ti4+ in the matrix whereas the site inhabitance was remunerated by Tb3+ ions, supporting that the anatase phase stays unaltered without generating any new deformities. Additionally, the Eu3+ ions decidedly changed the conduction band minimum of TiO2, actually, Tb3+ ions contrarily conversion because of various vacant trap states in the band gap. Besides, the photoinduced electron transfer estimations show an efficient interfacial charge transfer for co-doped TiO2 (kET = 3.1 ns) contrasted with the bare TiO2 (2.6 ns). DSSCs based on Eu3+/Tb3+ co-doped TiO2 display higher efficiency (9.11%) than those for the bare TiO2 (7.20%) and the exclusively Eu3+ (8.01%) or Tb3+ (7.10%) doped samples, which is ascribed to the joined impact of a faster electron transportation and longer electron lifetime in the co-doped TiO2 film. This work may open another approach to further improve the performance of DSSCs by Eu3+/Tb3+ co-doping technique, advancing the development of DSSCs toward commercial applications.