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Cerium doped lutetium scandium orthoborate Ce3+:Lu0.8Sc0.2BO3 is a novel and promising inorganic scintillator. For the sake of better understanding its scintillation mechanism, several approaches were undertaken to locate the Ce3+ energy levels relative to the host. To estimate the energy position of Ce3+4f levels with respect to the valence band, X-ray photoelectron spectroscopy (XPS) was used. Furthermore, the photoluminescence decays as a function of temperature, a widely used technique, was utilized to find the relative positions of Ce3+5d levels to the conduction band. Finally, the Ce3+ energy levels in Lu0.8Sc0.2BO3 host was constructed, meanwhile, the effectiveness of the XPS technique to estimate the energy position of Ce3+ 4f levels relative to the conduction band was evaluated.