The study of limestone calcination under high CO2 pressure and high temperature has gained an extraordinary practical importance due to the recently emerged Ca looping technology for post combustion CO2 capture, which uses natural limestone (CaCO3) as precursor of the CO2 solid sorbent (CaO). A critical issue of this promising process is the necessity of producing CaO by calcination of limestone under high CO2 partial pressure. Experimental measurements on the kinetics of limestone calcination usually show that the rate of the endothermic calcination reaction is increased with temperature according to an Arrhenius law with an activation energy similar to the reaction enthalpy change. In situ microscopic observations have demonstrated that the reaction involves a crystallographic structural transformation of CaO, Calcination is started by chemical decomposition leading to the development of metastable CaO* nanocrystals after which CO2 is &sorbed while stable CaO cubic crystals grow. In calcination environments with low CO2 partial pressure P (as compared to the equilibrium pressure: P/P-eq << 1), desorption of CO2 and the exothermic structural transformation of CaO* to its stable CaO form occur extremely fast and do not play a role on the reaction kinetics, which is just determined by chemical decomposition. However, at high values of P/P-eq the reaction rate may be significantly influenced by the structural transformation above a critical temperature. As a main consequence, the reaction mechanism proposed in the present paper shows that, above a critical temperature, limestone calcination is characterized by a negative activation energy in agreement with the experimental results shown. (C) 2015 Elsevier Ltd. All rights reserved.