Light-emitting-diode (LED) encapsulants, such as epoxy and silicone resin, have a lower refractive index than YAG:Ce phosphor, and this is usually one of the major causes of LED inefficiency. To improve LED performance, a glass encapsulant is considered. In this study, the SiO2-B2O3-ZnO glass system containing La2O3 and WO3 was investigated as an encapsulant to minimize total internal reflection and to increase the light extraction efficiency of LED packages. The characterization of glass encapsulants was performed using a differential scanning calorimeter, a pycnometer, a prism coupler, X-ray photoelectron spectroscopy, and integrating spheres. The refractive index increased linearly with increasing molar volume of glass because La2O3 and WO3 act as modifiers in the glass, creating more nonbridging oxygen. The refractive index of glass increases with the content of La2O3 and WO3, which is attributed to the increase in polarizability of oxide ions in the glass. When the refractive index between glass and phosphor matched, light extraction efficiency was maximized because total internal reflection decreased.