Epitaxy layers of solid solution (ZnSe) 1-x-y (Si 2 ) x (GaP) y (0  х  0.03, 0  y  0.09) were grown up from the limited volume of tin solution-melting by method of liquid phase epitaxy. Profiles of distribution of components Ga, P, Zn, Se and Si in grown up epitaxy layers are defined. In spectrum of the photoluminescence of surface of the solid solution at 5 K 2 peaks of radiation are found out. They are probably caused by compounds Si 2 (1.67 eV) and GaP (2.21 eV). It has been shown that covalent coupling Si-Si and Ga-P cause impurity levels laying in the forbidden zone of the solid solution (ZnSe) 1-x-y (Si 2 ) x (GaP) y . Isotype heterojunction n-GaPn09) (without luminophor) gives red and yellow luminescence which is caused by electronic transitions from Si-Si and from Ga-P, taking place in tetrahedron lattice of the solid solution.