Utilization of carbon dioxide from industrial waste streams offers significant reductions in global carbon dioxide emissions. Solid oxide electrolysis is a highly efficient, high temperature approach that reduces polarization losses and best utilizes process heat; however, the technology is relatively unrefined for currently carbon dioxide electrolysis. In most electrochemical systems, the interface between active components are usually of great importance in determining the performance and lifetime of any energy materials application. Here we report a generic approach of interface engineering to achieve active interfaces at nanoscale by a synergistic control of materials functions and interface architectures. We show that the redox-manipulated interfaces facilitate the atomic oxygen transfer from adsorbed carbon dioxide molecules to the cathode lattice that determines carbon dioxide electrolysis at elevated temperatures. The composite cathodes with in situ grown interfaces demonstrate significantly enhanced carbon dioxide electrolysis and improved durability.