The Mn-doped titanate can lead to the remarkable chemical adsorption of CO2 uncovering the tremendous potential for direct high temperature CO2 electrolysis. Unfortunately, the application of this material is still limited by insufficient carbon dioxide splitting and electrocatalytic activity. This study reports the improved electrocatalytic activity and Faraday efficiency of composite cathode with exsolution of nickel nanocrystals on the surface of doped titanate for CO2 electrolysis. The electrical conductivity has been enhanced in the presence of metallic Ni in contrast to bare Mn doped titanate and further correlated to the electrochemical performance of the composite cathodes. Promising electrode polarization has been demonstrated based on the titanate with nickel nanoparticles and the Faraday efficiency is improved for the direct CO2 electrolysis at high temperatures. (C) 2014 Elsevier Ltd. All rights reserved.