The single crystal ZnSe:I sample was grown by the chemical vapor transport (CVT) method using iodine as the transporting agent. The iodine incorporates itself effectively as a donor in the lattice. The sample shows a 〈111〉 optical quality surface and has an absorption edge at 2.55 eV due to a deep impurity band nearly 0.15eV below the conduction band. The photoluminescence emission spectra of this crystal have been measured for its temperature dependence as well as for excitation energy dependence. The photoluminescence is in accordance with a donor-acceptor complex formation involving iodine activated donors and self-activated acceptors. The configuration coordinate model has been used to explain the temperature dependent changes in the peak position and the bandwidth of the emission band. The decrease in luminescence efficiency with increasing temperature is explained by using a simple model for thermal quenching. The activation energy at low temperature range (T<200K) is different from that at high temperature range (200K<T<300K).