Phase relations along the Li2O⋅2B2O3-Yb2O3⋅B2O3 polythermal section of the Li2O –B2O3–Yb2O3 system were investigated by differential thermal analysis, x-ray diffraction, and microstructural analysis. The state phase diagram of the Li2O⋅2B2O3-Yb2O3⋅B2O3 section is an eutectic system with invariant eutectic point corresponding to ∼0.2 mole fraction of Yb2O3⋅B2O3 and 800 °C. According to physico-chemical analysis, the Li2O⋅2B2O3-Yb2O3⋅B2O3 polythermal section is quasi-binary, allowing us to partially triangulate the Li2O-B2O3-Yb2O3 system. The borders of the glass formation region were defined in the Li2O⋅2B2O3-B2O3-Yb2O3⋅B2O3 concentration triangle. The vitreous samples showed a semiconducting nature.