Optical emission spectra are studied from the vapor produced by irradiation of polycrystalline CuCl, under vacuum, by pulsed excimer laser radiation at 248 and 308 nm. For fluences &fgr;≲0.4 J/cm2(intensityI≲20 MW/cm2), well‐resolved molecular CuCl emission bands and weak atomic Cu lines are observed. At higher fluences, the CuCl emission increases and develops into a broad continuum due to the broadening and overlap of the bands, whereas the Cu atomic line emission increases more rapidly. At even higher fluences (&fgr;≳1 J/cm2,I≳50 MW/cm2), the Cu atomic emission dominates the entire spectrum. A thermal equilibrium model is used to calculate the vibrational‐rotational temperature of the emitting CuCl molecules as a function of fluence by fitting the experimentally observed emission bands. Temperatures in the range 500<T<2000 K for fluences in the range 0.27<&fgr;<0.4 J/cm2were obtained.