Chalcogenide alasses in the GeS2Ga2S3-Ag2S pseudo-ternary system were prepared by melt-quenching technique. The structural evolvement of the glasses was studied by Raman spectroscopy. The Raman results show that the addition of AG(2)S involves the breaking Of [S3Ge-GeS3] ethane-like units and the formation of Ag-S ionic bonds. The results of differential scanning calorimetry (DSC) show that the glasses have relatively high-glass transition temperatures and good thermal stabilities. These GeS2-Ga2S3-Ag2S classes have a wide range of transmission approximately from 0.50 to 12.5 mu m. In addition, with the method of Maker fringe. SHG was observed in the 0.9GeS(2)-0.05Ga(2)S(3)-0-05Ag(2)S glass irradiated by an electron beam. The value of secondorder nonlinear optical susceptibility d is as large as 6.6 pml\ and the poling mechanism of electron beam irradiation was also discussed in this work.