Using containerless processing with an aerodynamic levitation furnace, LaO3/2–TiO2 binary glasses were synthesized in bulk form. Glass-forming region was found in the vicinity of eutectic point, which is approximately 29.5% LaO3/2 and 70.5% TiO2 in molar ratio. The glass transition temperature Tg and the crystallization onset temperature Tx of the obtained glasses were determined by differential scanning calorimetry. The thermal stability was evaluated by ΔT (=Tx − Tg). Our experimental results were compared with phase diagram of the LaO3/2–TiO2 binary system. Glass compositions with highest ΔT corresponded to single-phase compound of La4Ti9O24 and the eutectic point.