Emission and excitation spectra of undoped and Ln(3+) (Ln = Ce, Pr, Nd, Yb)-doped Lu0.8Sc0.2BO3 were studied by vacuum ultraviolet spectroscopy, and the X-ray excited luminescence spectra were measured as well at room temperature. The undoped specimen presented two different emissions upon excitation at energies in the vicinity of the band gap or with X-ray. The emission at the highest energy side, located at 4.77 eV, was ascribed to self-trapped exciton, which is anchored by electron capture around the Sc site. We also observed three broad emission bands at 4.43, 3.02, and 2.10 eV, which might be attributed to the trapped exciton, defect - related emissions, or both. Energy transfer processes to the doped lanthanide ions in Lu0.8Sc0.2BO3 via exciton state or sequential electron-hole capture are discussed. Finally, the energy level diagram for divalent and trivalent lanthanides in Lu0.8Sc0.2BO3 was constructed using the obtained spectroscopic parameters and the three parameters method (Dorenbos, P. J. Phys.: Condens. Matter 2003, 15, 8417).