Photoluminescence (PL) and thermally stimulated conductivity (TSC) data on high‐resistivity,p‐type CdTe single crystals are presented. The PL emission in these samples consists of two closely overlapping components peaking at approximately 1.47 and 1.49 eV. Thermal quenching of these signals reveals activation energies of ∼0.02 and ∼0.13 eV for the former component, and ∼0.11 eV for the latter. TSC signals at temperatures corresponding to those over which thermal quenching occurs are observed. The TSC peaks are due to hole release with activation energies which agree with those obtained from the thermal quenching studies. Etching of the samples removes surface damage caused by mechanical polishing. The surface damage produces nonradiative pathways by which electron‐hole recombination can take place without luminescence. A model based on free‐electron to trapped‐hole recombination is presented to account for the data. It is shown, from numerical solutions of the rate equations describing the model, that by explicitly incorporating into the model more than one hole state at which radiative recombination can occur, shifts in the emission energy during time‐resolved and intensity‐dependence studies can be expected.