We have investigated X-ray induced radioluminescence (XL) properties of Sm-doped fluorochlorozirconate (FCZ) glasses and glass-ceramics. The FCZ glass is a modified ZBLAN glass which shows a very high optical transmission over a wide spectral range. The glass matrix includes Sm3+-doped nanocrystals of BaCl2 after heat-treatment at temperatures above 250 °C. The glass-ceramic emits red light under UV and X-ray exposure. Since conventional Si-based photodetectors, e.g., CCDs, have the highest quantum efficiency to red light in general, the Sm-doped FCZ glass-ceramic plate can be a good candidate as a scintillator material for indirect radiation detection. Moreover, a very broad emission is present in the glass-ceramic around 300–500 nm, which is attributed to a self-trapped exciton (STE) emissions. The temperature dependence of X-ray induced luminescence and photoluminescence are very similar. The XL light yield is linearly proportional to the X-ray exposure rate for rates higher than 20 mR/s. For low exposure rates, emissions by Sm2+ are more sensitive than others, leading to a nonlinear response.