We have studied the scintillation properties of non-doped and Pr-doped BaO–B2O3–SiO2 glasses and glass-ceramics. The glass transition temperature (Tg), the temperature of crystallization onset (Tx), and the crystallization peak (Tp) were determined by differential thermal analysis. The glass-ceramics were obtained by heating at three different temperatures (Tg + 50 °C, Tx, and Tp). We confirmed that the X-ray diffraction peaks can be ascribed to the BaSiO3 crystalline phase in the glass-ceramic samples. In the X-ray-induced scintillation spectra, we observed the intrinsic luminescence of the host glass and luminescence due to the 4f–4f transition of Pr3+ ions. In addition, the 1% Pr-doped BaO–B2O3–SiO2 glass-ceramic with heating at Tg + 50 °C clearly showed luminescence in the wavelength range from 250 to 350 nm under X-ray excitation. Its photoluminescence (PL) decay time was estimated to be 26.28 ns and its luminescence is considered to be due to the 5f–4f transition of Pr3+ ions.