A rare-earth trihalide scintillator, CeBr3, in 1 cm edge cubic monocrystal form, is examined with regard to its principal luminescence and scintillation properties, as a candidate for radiation imaging applications. This relatively new material exhibits attractive properties, including short decay time, negligible afterglow, high stopping power and emission spectrum compatible with several commercial optical sensors. In a setting typical for X-ray radiology (medical X-ray tube, spectra in the range 50–140 kVp, human chest equivalent filtering), the crystal’s light energy flux, absolute efficiency (AE) and X-ray luminescence efficiency (XLE) were determined. Light energy flux results are superior in comparison to other four materials broadly used in modern medical imaging (slope of the linear no-threshold fit was 29.5). The AE is superior from 90 kVp onwards and reaches a value of 29.5 EU at 140 kVp. The same is true for the XLE that, following a flat response, reaches 9 × 10−3 at 90 kVp. Moreover, the spectral matching factors and the respective effective efficiencies (EE) are calculated for a variety of optical sensors. The material exhibits full compatibility with all the flat-panel arrays and most of the photocathodes and Si PMs considered in this work, a factor that proves its suitability for use in state-of-the-art medical imaging applications, such as CT detectors and planar arrays for projection imaging.