A novel combined single chamber solid electrolyte plus fixed bed reactor configuration was developed for the simultaneous production of H-2 and C-2 hydrocarbons from a humidified CH4 atmosphere. Hence, a Pt/YSZ/Ag solid electrolyte cell was placed on the top of an active oxidative coupling catalyst powder bed Ce-Na2WO4/SiO2. H-2 was produced via steam electrolysis in a Pt cathode of the solid electrolyte cell (H2O + 2e(-) -> H-2 + O2-). Simultaneously, the produced O(2-)ions were electrochemically pumped to the Ag anode, leading to the C-2, production, via oxidative coupling of CH4 (4CH(4) + 3O(2-) -> C2H4 + C2H6 + 3H(2)O + 6e(-)). Additionally, non-reacted O2- molecules desorbed to the gas phase (2O(2-) -> O-2+4e(-)) and reacted with CH4 in the catalyst bed leading to an increase of C-2s yield. The influence of different reaction parameters was investigated together with long-term reaction experiments, confirming the stability of this configuration for its practical application. The obtained results demonstrated that the addition of an active catalyst bed strongly enhances both: the efficiency of the single chamber steam electrolysis and the oxidative coupling process. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.