We appreciate that EPSRC-EP/P007821/1 and LERG for funding support.The demand for clean and sustainable energy has garnered great interest in new energy materials. Among them, high temperature proton-conducting perovskite oxides are, or can be widely used in clean energy applications (including fuel cells, electrochemical reactors, solid-state separators and supports of catalytic components via various reduction and oxidation reactions) in the intermediate temperature range. The control of defect chemistry is the main strategy to fine tune properties for these applications. This review provides a critical discussion about non-stoichiometry-structure-property relation in terms of structure distortions by intrinsic octahedral titling and extrinsic acceptor doping, chemical stability, hydration behavior, transport properties, and catalytic effects in some typical classes of proton conducting perovskites and perovskite-related derivatives. A good understanding of A-site and B-site non-stoichiometry is also given to allow the perovskite structure with desired properties.PostprintPeer reviewe