The characteristic of a number of oxide materials, which include BaCeO3-systems, is their ability to show the proton conductivity along with oxygen-ion conductivity. Such atypical behavior for other oxides attracts great interest in theoretical and experimental solid state electrochemistry. The present review aims at: (a) summarizing the evolution of new functional BaCeO3-based materials with respect to their properties, and properties' optimization (importance of ceramics' technology preparation, structural and thermodynamic stability of materials, enhanced ionic conductivity of electrolytes with low electronic contribution, thermal and chemical compatibility with other oxide components), and (b) examining the possibility of their application in various solid oxide electrochemical devices. (C) 2013 Elsevier Ltd. All rights reserved.