In this work, we explored the possibility of growing a substitutional solid solution (GaAs)1−x(ZnSe)x with an ordered array of nanosize crystals on GaAs (100) substrates. Grown epitaxial films were investigated by the X-ray diffraction analysis method. The chemical composition of the grown epitaxial films was determined by a X-ray microanalyzer, along the thickness of the epitaxial layer. The photoluminescence spectrum was studied and a peak is observed at λmax = 465 nm, corresponding to the width of the band gap of zinc selenide EZnSe = 2.67 eV, which is apparently due to the nanocrystals ZnSe, disposed in the surface region of the epitaxial film of a solid solution (GaAs)1−x(ZnSe)x. Size of nanocrystals were evaluated by an atomic force microscopy.