Present study investigates the response of various coloured variants of natural fluorite (CaF₂) to 10 MeV electron beam irradiation at accumulated dose of 5–10 MGy. The fluorite specimens did not show any post irradiation radioactivity. However, after irradiation the specimens developed purple colouration of different shades depending on the dose. In-depth characterization of the as-received and irradiated specimens using XPS and Raman spectroscopy confirm the relocation of fluorine (F) anions at interstitial sites and formation of metallic calcium (Ca). The calculated displacement cross sections for F and Ca indicate that it is easier to form fluorine anion interstitials within lattice structure. However, the estimated lower fraction of interstitial fluorine (~14%) as compared to metallic Ca (>50%) is attributed to their surface diffusion and desorption. Electron irradiation was found to cause photoluminescence quenching in all the CaF₂ specimens that is likely caused by a radiation-induced formation of competing recombination channels.