The GaSe single crystals are composed by planar Se-Ga-Ga-Se type packages bonded by polarization forces. The packages are arranged in the way that between them the fissure are formed in which the atoms and molecules easily can interspersed. Because of the strong ionic-covalent bonds between atoms within layered packing, the atoms of uncontrollable impurities as well as the dopants in a small concentration reduce the structural defects of basic compound, but the surplus of them is stored between packages. Despite the fact that the valence bonds of Se atoms at the surface of crystal are closed, at the height temperatures the atoms stocked between packages forms chemical compounds with selenium atoms from both packages. In this way the Se contribute to anisotropy of physical properties of material. If the Europium is used as the dopant in quantities till 0.025 at.%, it can reduce defects in the metal sub-lattice, contributing in this way to amplification of excitonic processes in GaSe. At concentrations of about 0.49 at.%, of Eu the atoms sits inside the packages and could have 6 Ga atoms as first neighbors. At the same time the Eu atoms localized between packages have in the first coordination sphere 6 Se atoms. The photoluminescence (PL) spectra at the temperatures between 78 K and 300 K of GaSe crystals doped with 0.49 at.% of Eu, CdSe-GaSe and CdSe-GaSe:Eu nanolamellar composites is studied in the paper. The maximum of intensity of dominant band in PL spectrum at 78 K is caused by Eu3+ ions in GaSe corresponds to energy of 2.180÷2.190 eV. The treatment of GaSe and GaSe:Eu single crystals in Cd vapours at the temperature of 830K leads to formation of CdSe and respectively CdSe:Eu nanocrystalline layer onto surface. At the same time, at the interface of elementary packages are formed CdSe (CdSe:Eu) layers. In this way the CdSe-GaSe and, respectively, CdSe- GaSe:Eu nanolamellar composite is formed. The PL spectra of CdSe-GaSe and CdSe-GaSe:Eu composites have a mixt structure. This particularity of structure is caused by superposition of PL emission bands of GaSe and CdSe from composite and respectively of luminescence centers of Eu3+ ions. Also the influence of intercalated atoms on the structure of PL spectra as a function of intercalation temperature and concentration of Eu atoms (in ε-GaSe single crystals) is analyzed in the paper.