The ability of MCFCs as carbon dioxide concentrator is an alternative solution among the carbon capture and storage (CCS) technologies to reduce the CO2 emission of an existing plant, providing energy instead of implying penalties. Moreover, the fuel flexibility exhibited by MCFCs increases the interest on such a solution. This paper provides the performance characterization of MCFCs operated in CCS configuration and fed with either natural gas or biogas. Experimental results are referred to a base CCS unit constituted by a MCFC stack fed from a reformer and integrated with an oxycombustor. A comparative analysis is carried out to evaluate the effect of fuel composition on energy efficiency and CO2 capture performance. A higher CO2 removal ability is revealed for the natural feeding case, bringing to a significant reduction in MCFC total area (-11.5%) and to an increase in produced net power (+13%). Moreover, the separated CO2 results in 89% (natural gas) and 86.5% (biogas) of the CO2 globally delivered by the CCS base unit. Further investigation will be carried out to provide a comprehensive assessment of the different solutions eco-efficiency considering also the biogas source and availability. (C) 2016 Elsevier B.V. All rights reserved.