A glass-forming domain is found and studied within Bi2O3-Sb2O3-TeO2 system. The glasses composition were obtained in pseudo-binary xSbO(1.5), (1-x)TeO2 for 0.05 a parts per thousand currency sign x a parts per thousand currency sign 0.20. The constitution of glasses in the system Sb2O3-TeO2 was investigated by DSC, Raman, and Infrared spectroscopy. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated based Infrared and Raman studies and showed the transition of TeO4, TeO3+1, and TeO3 units with increasing Sb2O3 content. XRD results reveal the presence of three crystalline: gamma-TeO2, alpha-TeO2, and SbTe3O8 phases during the crystallization process. The density of glasses has been measured. The investigation in the ternary system by the solid state reaction using XRD reveals the existence of a solid solution Bi1-x Sb1-x Te-2x O-4 isotopic to BiSbO4 with 0 a parts per thousand currency sign x a parts per thousand currency sign 0.1.