High temperature co-electrolysis of steam/CO2 mixtures using solid oxide cells has been proposed as a promising technology to mitigate climate change and power fluctuation of renewable energy. To make it viable, it is essential to control the complex reacting environment in their fuel electrode. In this study, dominant reaction pathway and species transport taking place in the fuel electrode and their effect on the cell performance are elucidated. Results show that steam is a primary reactant in electrolysis, and CO2 contributes to the electrochemical performance subsequently in addition to the effect of steam. CO2 reduction is predominantly governed by thermochemical reactions, whose influence to the electrochemical performance is evident near limiting currents. Chemical kinetics and mass transport play a significant role in co-electrolysis, given that the reduction reactions and diffusion of steam/CO2 mixtures are slow. The characteristic time scales determined by the kinetics, diffusion and materials dictate the cell performance and product compositions. The fuel electrode design should account for microstructure and catalysts for steam electrolysis and thermochemical CO2 reduction in order to optimize syngas production and store electrical energy effectively and efficiently. Syngas yield and selectivity are discussed, showing that they are substantially influenced by operating conditions, fuel electrode materials and its microstructure. (C) 2015 Elsevier B.V. All rights reserved.