Phase and morphology evolution of CaCO3 precipitated during carbonation of lime pastes via the reaction Ca(OH)(2) + CO2 -> CaCO3 + H2O has been investigated under different conditions (pCO(2) a parts per thousand 10(-3.5) atm at 60 % RH and 93 % RH; pCO(2) = 1 atm at 93 % RH) using XRD, FTIR, TGA, and SEM. Simulations of the pore solution chemistry for different stages and conditions of carbonation were performed using the PHREEQC code to investigate the evolution of the chemistry of the system. Results indicate initial precipitation of amorphous calcium carbonate (ACC) which in turn transforms into scalenohedral calcite under excess Ca2+ ions. Because of their polar character, scalenohedral faces (type S) interact more strongly with excess Ca2+ than non-polar rhombohedral faces (type F), an effect that ultimately favors the stabilization of faces. Following the full consumption of Ca2+ ions and further dissolution of CO2 leading to a pH drop of the pore solution, scalenohedra are subjected to dissolution. This eventually results in re-precipitation of rhombohedra at close-to-neutral pH. This crystallization sequence progresses through the carbonated depth with a strong dependence on the degree of exposure to CO2, which is controlled by the carbonated pore structure governing the diffusion of CO2. Both the carbonation process and the scalenohedral-to-rhombohedral transformation are kinetically favored under high RH and high pCO(2). Supersaturation plays a critical role on the nucleation density and size of CaCO3 crystals. These results have important implications in understanding the behavior of ancient and modern lime mortars for applications in architectural heritage conservation.