Emission from the plasma generated when a pulsed CO2 laser is used to evaporate dielectric materials is analyzed in the 200–900 nm region by means of an optical multichannel analyzer. Atomic spectra consisting of excited neutral and singly, doubly, and triply ionized species were observed from laser irradiation of Al2O3, SiO2, ZnO, PbF2, TiO2, and HfO2. Emission from the B–X transition of AlO was observed under vacuum conditions becoming more intense in the presence of added gases. Assuming local thermal equilibrium, plasma temperatures were calculated using the emission intensities of several selected atomic species. Possible effects of the observed phenomena on the properties of thin films deposited by laser‐assisted deposition are discussed.