Scintillator glasses have the potential for X-ray imaging owing to their low production cost, controllable shape and size, and uniform ion-doping concentration. In this study, Tb3+-doped and Ce3+/Tb3+-co-doped oxyfluoride scintillator (C4T9) glass samples were fabricated by high-temperature melting and quenching. In addition, the luminescence properties of the glass samples and the discrepancy in the energy transfer mechanism between Ce3+ and Tb3+ under ultraviolet (UV) light and X-ray excitation were investigated. The C4T9 glass sample showed excellent integral scintillation efficiency of 84.1% for commercial Bi4Ge3O12 (BGO) crystals. The spatial resolution of the C4T9 glass sample was higher than that of the commercial BGO crystal with 42.29 mGy s−1 X-ray irradiation, reaching 16 lp·mm−1. C4T9 glass is expected to become a key material in medical imaging, safety inspection, industrial inspection, and other fields.