The GaSe single crystals are composed by plane packages of Se-Ga-Ga-Se type packages orientated perpendicularly to C6 crystallographic axe. The chemical bonds of selenium atoms on the surface are closed which causes poor interaction between wraps. At the same time the atoms are bound with strong ionic-covalent forces inside the elementary packages. The structural anisotropy of this compound determines the location of the impurity atoms. The stoichiometric excess of dopant atoms as well as the dopant is accumulated in the space between packages. The dopant atoms of Eu at the interface of GaSe layered packing are surrounded by six atoms of Se. However, the Eu atoms are located inside the layered packages and are surrounded by six Ga atoms. The Eu can form two types of ionizing centers in GaSe. The interplay of Zn atoms between layered packing change the structure of centers between layered packages. The GaSe crystals doped with 0.49 at. % of En obtained by treatment at 753 K and 853 K in Zn vapor are studied. The structural composition of the samples was analyzed by XRD method on DRON-2 type installation. The analysis of diffractogram shows that the obtained material is a composite which consists of ZnSe and GaSe:Eu crystallites. The sizes of ZnSe and GaSe:Eu crystallite from composite was approximated from the analysis of diffraction lines contour of the plane of crystallites assemblies and have the dimension of 25-35 nm. The PL spectra of GaSe:Eu crystallites contain radiative emission band of Eu3+ ion and impurity band in GaSe at 1.94 eV. The PL spectrum of the composite obtained by treatment at 750 K for 6 h is composed of at least four bands with the maximums in the energy range from 1.92 eV to 3.05 eV. The PL spectrum of composite at 78 K covers the spectral range of GaSe and ZnSe compounds. When the temperature of treatment was increased form 750 K to 850 K, the major changes in the PL structure at 78 K and the attenuation of emission band take place. These issues are characteristic to ZnSe crystal. Meanwhile the emission band is amplified in the orange region with a maximum at 2.045 eV. This band was identified as radiative transition of Eu3+ ions from the 5D0 excited level to one of fundamental states of this ion. The analysis of the structure of PL spectra of composites and the temperature dependence of their structure is analyzed.