The impact of membrane type and electrolyte composition for the electrochemical generation of synthesis gas (CO + H-2) using an electrolysis cell containing a Ag gas diffusion cathode is presented. Changing from a cation exchange membrane to an anion exchange membrane extended the cell operational time at low cell voltages (E-cell) without impacting product composition. The use of KOH as the catholyte decreased the E-cell and resulted in a minimum electrolyte cost reduction of 34%. The prime factor in determining operational time at low E-cell was the ability to maintain a sufficiently high anolyte pH. (C) 2012 The Electrochemical Society. [DOI:10.1149/2.010204esl] All rights reserved.