In this study, Ce-doped La2O3–Al2O3 glasses were prepared by the levitation method, a containerless glass-making method, and their optical and radiation-induced luminescence properties were investigated. From the Raman spectral analysis, it was observed that an increase in La2O3 content correlates with an increase in the number of non-bridging oxygen (NBO) atoms arising from the reduction in the number of AlO4 units, and a decrease in the number of high-coordination aluminum species such as AlO5 and AlO6. Variations in glass composition also affect the luminescent properties. In samples with lower La2O3 content, two types of emission were observed: one from typical Ce3+ ions and the other from Ce–O associates. However, as the La2O3 content increased, the emission from Ce–O associates diminished and ultimately disappeared. In the scintillation spectra, the luminescence from Ce–O associates was barely observed, whereas that from the 5d–4f transition of Ce3+ was dominant. Since the emission intensity is affected by the number of carrier traps, the Ce-doped La2O3–Al2O3 glass can function as both a scintillator and a dosimeter material by optimizing the glass composition.