The crystal structure as well as the optical properties in the band gap region of (CuInTe2)1‐x(2 ZnTe)x solid solution single crystals grown by directional freezing have been studied. The lattice constants exhibit a linear dependence on crystal composition. The chalcopyrite‐sphalerite phase transition was observed between x = 0.3 and x = 0.4°. The variation of the band gap with respect to crystal composition can be described by a quadratic expression.