To elucidate the linear energy transfer (LET) effects on the scintillation properties of a self-activated scintillator, CeF3, from an aspect of excited state dynamics, we observed the scintillation time profiles of CeF3 under irradiations of pulsed beams having different LETs. The initial decay was faster for higher LET, which in line with the LET dependence observed for other self-activated scintillators in previous studies. The faster decay at higher LET can be explained in terms of competition between the scintillation caused by 5d–4f transition of Ce3+ ions and quenching owing to the interaction between excited Ce3+ ions close to each other.