The structure, ultraviolet (UV) transparency, luminescence, and scintillation of CeO2-doped (0.1 mol%) borosilicate glasses containing Sb2O3, SnO2 or P2O5 were investigated. Glasses were prepared by melt quenching in air and characterized by several spectroscopy techniques: Raman scattering, optical absorption, photoluminescence (PL), fluorescence lifetime, thermoluminescence, and radioluminescence. Raman scattering results presented three major groups of vibrational modes, within 230–850 cm−1, 850-1250 cm−1, and 1250-1600 cm−1. Luminescence was dominated by a broad band centered at around 360–380 nm, depending on the chemical composition of the glass. Photoluminescence presented a dominant (96–98%) fast decay time of 36–40 ns that was ascribed to Ce3+. The P2O5-containing glass showed the highest scintillation output under X-ray excitation.