Abstract Photoluminescence of X-irradiated CaF 2 :Co single crystals is reported. The emission spectrum shows four peaks at 505, 550, 640 and 685 nm, all of them with an excitation band at 275 nm. The same emission spectrum, plus a band at 280 nm, is found in X-ray excited luminescence measurements. Thermoluminescence of 80 K X-irradiated crystals gives a glow curve with five peaks at 100, 125, 145, 190 and 225 K. The spectral distribution of these glow peaks is similar to that of the X-ray excited luminescence. The 280 nm band is associated with electron—hole recombination. The other four bands are associated with electron transitions among excited states of Co 2+ produced by recombination of holes and Co + -ions created by X-irradiation.