Deep centres of ZnS:Ga single crystals are investigated by the following methods: impurity electroabsorption, photoconductivity, and luminescence. From the measurements the spectrum of deep levels is determined. It is assumed that the luminescence spectrum of the investigated samples is in general determined by the radiative recombination of donor—acceptor pairs, where the pair consists of the complex (VZnGaZn)′ as acceptor and of gallium on zinc site as donor.