The thaumasite was obtained using two routes: 1) from the exposure of Portland limestone cement pastes, with 30% limestone, to 4% magnesium sulfate solution for 3 months at 7°C, 2) through the carbonation of an ettringite–sodium silicate mix at 7°C, followed by the rise of pH with lime. The phases formed were examined by XRD, infrared spectroscopy, and scanning electron microscopy. The thaumasite after 2 months of exposure of the limestone cement to sulfate solution was formed. It is prevented by the addition of specific chemicals that reduce calcium and sulfate ions. The prevention is confirmed by microstructure analysis and compressive strength measurement. The mechanism of thaumasite formation is explained by the formation of an intermediate phase composed of a carbonated silica gel, which incorporates relicts of the decomposed ettringite. This phase transforms to thaumasite through the liquid phase pH rise by lime. The results support previous literature published as early as 2003 and suggested the formation of an intermediate phase which was the thaumasite, the product of sulfate attack. The present work was defining the nature of this phase. This phase was not detected in the first route of the Portland limestone cement system because of the rapid rate of lime supply, from the alite hydrolysis.