Significant anisotropy of the optical transmission associated with the exponential increasing of the absorption coefficient and the anisotropy of the photoluminescence were found in ZnIn2S4 and ZnIn2S4:Cu single crystals. It was shown that the peculiarities of the investigated photoluminescence spectra are associated with optical transitions involving donor and acceptor levels. The possibility was found to control the spectra’s shape and intensity using doping and variation of the technological parameters to allow preparing ZnIn2S4 single crystals with alternation of three and one packet polytypes.