A GaTe–CdTe composite was obtained by thermal treatment at 1020 K of GaTe single crystals in Cd vapor atmosphere. The composite photoluminescence, photoconductivity, and composition are studied in this work. The photosensitivity and photoluminescence band structure are determined for both the primary crystals and the composite. The CdTe crystallites create, in the GaTe bandgap, recombination and trapping levels, which determine the structure of the photoluminescence spectra and the spectral range of composite photosensitivity. The photoluminescence spectrum of the composite at 80 K contains characteristic bands of both composite components, GaTe and CdTe. From the analysis of thermally stimulated luminescence curves, the energies of the electron trapping levels in the composite are determined.