Scintillators that can absorb high-energy photons and convert them into low-energy visible photons are used extensively in fields, including nondestructive inspection, security inspection, and medical imaging. Aiming at the inadequacy of time-consuming and high cost in the preparation process of traditional scintillator crystals, Sn²⁺-doped borosilicate glasses are synthesized successfully through the traditional melt-quenching approach in this study. The transmission, excitation, and ultraviolet (UV) stimulated emission spectra, X-ray excited luminescence (XEL) spectra, and decay curves of the materials are systematically investigated. The experimental findings that correct heat treatment can efficiently improve the fluorescence intensity of UV and XEL of the sample, and the XEL intensity of the optimal sample reaches 25.1% of that of commercial Bi₄Ge₃O₁₂ crystal. Furthermore, the transmittance of the sample decreases only moderately under various power X-ray excitation. In addition, it can be restored to the initial level after the thermal treatment again. The synthesized samples endow remarkable fluorescence properties of ultraviolet excitation and X-ray irradiation that have promising potential in X-ray imaging and other fields.