We report on a detailed investigation on the temperature-dependent behavior of photoluminescence from molecular beam epitaxy (MBE)-grown chlorine-doped ZnSe epilayers. The overwhelming neutral donor bound exciton ((ClX)-X-0) emission at 2.797 eV near the band edge with a full-width at half-maximum (FWHM) of similar to 13 meV reveals the high crystalline quality of the samples used. In our experiments, the quick quenching of the (ClX)-X-0 line above 200 K is mainly due to the presence of a nonradiative center with a thermal activation energy of similar to 90 meV, The same activation energy and similar quenching tendency of the (ClX)-X-0 line and the I-3 line at 2.713 eV indicate that they originate from the same physical mechanism. We demonstrate for the first time that the dominant decrease of the integrated intensity of the I, line is due to the thermal excitation of the "I-3 center"-bound excitons to its free exciton states, leaving the "I-3 centers" as efficient nonradiative centers. The optical performance of ZnSe materials is expected to be greatly improved if the density of the "I-3 center" can be controlled. The decrease in the luminescence intensity at moderately low temperature (30-200 K) of the (ClX)-X-0 line is due to the thermal activation of neutral-donor-bound excitons ((ClX)-X-0) to free excitons.