The aim of this study was to experimentally assess the luminescence efficiency of a cerium fluoride (CeF3) inorganic scintillator in crystal form as a possible alternative to high-luminescence but hygroscopic cerium bromide (CeBr3). The experiments were performed under typical diagnostic radiology X-rays (50–140 kVp). Parameters such as the crystal’s absolute luminescence efficiency (AE) and the spectral matching with a series of optical detectors were examined. The replacement of bromine with fluorine appeared to drastically reduce the AE of CeF3 compared to CeBr3 and other commercially available inorganic scintillators such as bismuth germanate (Bi4Ge3O12-BGO). CeF3 reaches a maximum luminescence efficiency value of only 0.8334 efficiency units (EUs) at 140 kVp, whereas the corresponding values for CeBr3 and BGO were 29.49 and 3.41, respectively. Furthermore, the emission maximum (at around 313 nm) moved towards the lower part of the visible spectrum, making CeF3 suitable for spectral coupling with various photocathodes and photomultipliers applied in nuclear medicine detectors, but completely unsuitable for spectral matching with CCDs and CMOS. The obtained luminescence efficiency results denote that CeF3 cannot be applied in medical imaging applications covering the range 50–140 kVp; however, examination of its luminescence output in the nuclear medicine energy range (~70 to 511 keV) could reveal possible applicability in these modalities.