The emission spectra of the CeFa crystals in UV-visible region and their temperature dependence in the range of 6-453K under UV, VUV excitation as well as their excitation spectra (4-25eV) have been studied. The 350nm emission band from perturbed Ce3+ can be excited by 295.2 and 302.4 nm emissions from the regular Ce3+. The 350 nm emission band, in tu, can excite the emission bands centered at 470 and 535 nm caused by some defects below room temperature. These results show that there is a cascade energy transfer process from regular Ce3+to quenching centers via perturbed Ce3+ and defect centers in the CeF3. Meanwhile, thermoluminescence, giving peaks at about 240 and 300° C has been discovered, and the corresponding deep traps with depth～ 1 eV are found to be a kind of quenching center for CeF3 luminescence at room temperature.