Emission spectra of GaTe single crystals in the range of 1.90–1.38 eV have been analyzed at different temperatures and excitation intensities by photoluminescence, photoluminescence excitation, and selective photoluminescence. A decrease in band gap energy with an increase in temperature was obtained from the redshift of the free exciton recombination peak. The energy of longitudinal optical phonons was found to be 14±1 meV. A value of 1.796±0.001 eV for the band gap at 10 K was determined, and the bound exciton energy was found to be 18±0.3 meV. The activation energy of the thermal quenching of the main recombination peaks and of the ones relating to the ionization energy of impurities and defects was analyzed. The results obtained show the existence of two acceptor levels with ionization energies of 110±5 and 150±5 meV, respectively, and one donor level with an ionization energy of 75±5 meV. The study of chemical composition by inductively coupled plasma-optical emission spectroscopy and x-ray energy dispersion spectroscopy shows the existence of Na, Li, and Si. Sodium and lithium impurities could be associated with acceptor levels at gallium substitutional sites, and silicon ones with a donor level at Ga sites, whose vacancies can also be involved in these electronic levels.