Phototransferred thermoluminescence (PTTL) of natural fluorite induced by 470 nm blue-, 525 nm green-, and 870 nm infrared light is reported. Although its conventional thermoluminescence (TL) glow curve measured during heating to 600 °C has six peaks, only five are reproduced under phototransfer. One of them corresponds to a hole trap. The sixth peak counterintuitively increases in intensity with illumination in a change suggestive of competition effects involving deep electron traps. The dependence of PTTL intensity on duration of illumination for each PTTL peak is analyzed using phenomenological and kinetic models as systems of acceptors and donors with the number of the latter informed by experiment. The intensity of PTTL increases with the temperature of illumination with an activation energy of thermal assistance of 0.14 ± 0.01 eV and decreases at elevated temperatures with an activation energy of thermal quenching of 1.1 ± 0.3 eV. The long-term behavior of time-response profiles and the interaction of holes with stimulated electrons as studied by stability theory show unstable critical points. Supplementary tests show that exposing CaF2 to UV illumination achieves the same effect as beta irradiation, and any resultant peaks relate to conventional TL rather than phototransfer.