This study investigates the coupled substitution of metakaolin and limestone in Portland cement (PC). The mechanical properties were studied in mortars and the microstructural development in pastes by X-ray diffraction, thermogravimetry analysis, mercury intrusion porosimetry and isothermal calorimetry. We show that 45% of substitution by 30% of metakaolin and 15% of limestone gives better mechanical properties at 7 and 28 days than the 100% PC reference. Our results show that calcium carbonate reacts with alumina from the metakaolin, forming supplementary AFm phases and stabilizing ettringite. Using simple mass balance calculations derived from thermogravimetry results, we also present the thermodynamic simulation for the system, which agrees fairly well with the experimental observations. It is shown that gypsum addition should be carefully balanced when using calcined clays because it considerably influences the early age strength by controlling the very rapid reaction of aluminates. (C) 2012 Elsevier Ltd. All rights reserved.