The electronic structure of Yb³⁺-doped BaPrO₃ (BaPr_1-xYb_xO_3-δ) has been studied by resonant photoemission spectroscopy and X-ray absorption spectroscopy (XAS). The O 1s XAS spectra exhibit that the conduction band consists of Pr 4f and Ba 5d states. The valence band is mainly composed of the O 2p states hybridized with Pr 4f and Pr 5d states. The valence band shifts to the lower binding energy side with Yb³⁺ concentration. The Pr 4f state has the mixed-valent states of Pr⁴⁺ and Pr³⁺. The intensities of Pr⁴⁺ and Pr³⁺ states rapidly decrease with increasing Yb³⁺ concentration. These results may contribute to the change of charge transfer from O 2p to Pr 4f states in the ground state with oxygen vacancies and Yb³⁺ substitution.