The aim of this work is to investigate how SO2 can affect MCFC performance and to discover the possible mechanisms involved in cathode sulphur poisoning, specifically considering the possible use of MCFCs in CCS (Carbon Capture and Storage) application. The different contributions of cathodic, anodic and electrolyte reactions have been considered to get a complete picture of the evolution of performance degradation. Experimental tests have been performed at the Fuel Cell Centre laboratories of Korea Institute of Science and Technology (KIST) thanks to 100 cm(2) single cell facilities and comparing results using both an optimized gas for laboratory conditions and a gas composition that simulates MCFCs when running in a Natural Gas Combined Cycle (NGCC) power plant. Polarisation curves, endurance tests, impedance measurements and gas analyses have been carried out to support the investigation. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.