δ-Bi2O3, a material with a fluorite-type structure, is one of the best solid-state oxygen-ion conductors. It is a high-temperature form that cannot be quenched to room temperature. However, doping with small amounts of transition metal oxides preserves the δ-Bi2O3 structure at low temperature and retains its anionic conduction properties. The Bi2O3–MoO3 materials are interesting because of their functional properties, chiefly as catalysts and as good ionic conductors. All the phases in this system are related to the fluorite structure except Bi2MoO6 which shows an Aurivillius-type structure.