Various structural families have been reported to support oxide ion conductivity; among these, perovskite conductors have received particular attention. The perovskite structure is generally composed of a framework of corner-sharing octahedral units. When the octahedral units share their faces, hexagonal perovskites are formed. Mixed combinations of corner-sharing and face-sharing octahedral units can give rise to a variety of hexagonal perovskite derivatives. However, the ionic conducting properties of these materials have not been well explored. In this feature article, we review the conducting properties of the most significant hexagonal perovskite derivatives, with special focus on Ba3MM'O8.5. Ba3MM'O8.5 is the first hexagonal perovskite derivative to exhibit substantial oxide ion conductivity, and here we outline the structural features that are key for the oxide ion conduction within this system. The results demonstrate that further investigation of hexagonal perovskite derivatives could open up new directions in the design of oxide ion conductors.
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