Glasses composed of ternary components (35 – x)Sb2O3–xBi2O3–65P2O5(0 ⩽ x ⩽ 20 mol%) have been prepared and investigated as a potential alternative to lead-free glass for low temperature applications. Their structural properties were studied by Infrared Spectroscopy IR and Differential Thermal Analysis DTA. Results from the IR showed that Sb3+and Bi3+were responsible for glass network structure, which was supported by the diversification of density ρ and molar volume Vmwith an increasing amount of Bi2O3. Glass transition temperature Tg, thermal stability, and coefficient of thermal expansion increased after substitution of Bi2O3for Sb2O3within the range of 0 mol% to 20 mol%. The water durability decreased and then increased; it could be attributed to the corrosion resistant P–O–Sb bonds. A typical sample of 25Sb2O3–10Bi2O3–65P2O5possesses excellent properties and can be a promising candidate for further applications.