AbstractCement production process features intrinsically large CO2 emission due to the decomposition of limestone by calcination reaction and to fuel combustion, necessary for sustaining the endothermic calcination process and the formation of clinker. Conventional approaches to CO2 emission reduction in cement plants are based on post-combustion capture with chemical solvents, requiring a substantial energy consumption for regeneration, or oxycombustion in the cement kiln, involving a deep redesign of the plant. The aim of this work is investigating the application of Molten Carbonate Fuel Cells in cement plants for CO2 capture from the plant exhaust gases, using the fuel cells as active CO2 concentrators of combustion flue gases and eventually obtaining a purified CO2 stream through a cryogenic process. A novel configuration with MCFCs added along the exhaust line has been assessed by means of process simulations. The results show a remarkable potential in terms of equivalent avoided CO2 emissions (exceeding 1000g/kWh), high share of CO2 avoided (up to about 70%) and low energy penalties.