There is a number of cases where chalcogenic glass semiconductors have to be practically used as optical materials. Therefore, their transparence characteristics have to include both the visible and close infrared part of the spectrum, particularly the wavelengths of He-Ne (0.6328#m) and CO2 (10.6#m) lasers. Analysing the literature data [1,2] it was possible to find out that there are only a few glass compositions from binary As-S systems which are vitrous at 0.63 and 10.6 #m. However, thermodynamic parameters and conditions under which these materials are synthesized prevent the formation of optically homogeneous glasses of greater dimensions with predetermined physical chemistry and optical characteristics. Therefore, in order to obtain more favourable technological characteristics of glass, other components are added, first of all germanium and antimony. It has been found that glasses from the Ge-As-S system are characterized by the large value of the coefficient of linear expansion, while those from Sb-As-S system are characterized by the significant tendency of crystallization which also prevents synthesis of optically homogeneous glasses of greater dimensions.Systematic investigations of the processes of glass formation, chemical interactions and formation of glass structures in the complex M-AV-BVI-c w~ systems (where M is an arbitrary element from the Periodic Table of Elements AV-p, As, Sb, Bi; BvI-S, Se, Te; CVU-C1, Br, I) have indicated the system Ge-As-S-I as the most optimal one from the physico-technological point of view. The combination of the Ge20ASl4Ss2Ii4 type proved to be particularly optimal [3]; even sulphur is replaced by selenium. After this substitution the energy gap calculated from electrical measurements is changed by more than 0.40 eV.In order to investigate the general physicaltechnology characteristics and the possibilities of obtaining the materials with a pre-determined energy gap on the basis of sulphur and selenium content variation, five-component samples of the Ge20As14(SexSl_~)52Ii4 type were synthesized.