The synthesis and properties of the vitreous system (0.75-x)Ga2S3-0.25Na(2)S-xCsCl, with x varying from 0.1 to 0.2, are presented. Thermal, optical, and structural properties such as density, viscosity, thermal expansion coefficient, glass transition temperature, softening point temperature, refractive index, and absorption coefficient were measured using several techniques: X-ray diffraction, Raman scattering, differential thermal analysis, thermal mechanical analysis, and absorption spectroscopy. This glass system presents a high third-order non-linear optical susceptibility that can be significantly increased by increasing the CsCl content without affecting the low phonon frequency.