Transparent and high refractive index 0.2La2O3·0.8WO3 glass was prepared in bulk form using containerless processing. The glass transition temperature, crystallization onset temperature, and melting temperature were 553°C, 594°C, and 1043°C, respectively. The glass was colorless and widely transparent, in the visible to infrared region, indicating that the valence state of the W ion was 6. The refractive index was 2 in the visible range, and the Abbe number estimated from the Drude–Voigt relationship was 24. These results indicate that the La2O3–WO3 glass would be useful for optical applications in the visible to infrared region.