The results obtained in an experimental study that analyzed the hydration process of ordinary Portland cement (OPC) paste with 20% addition of thermally treated kaolin (TTK) are presented. The kaolin was thermally treated between 500 and 900°C. Resulting pastes were analyzed by x-ray diffraction (XRD), differential thermogravimetry (DTG) and scanning electronic microscopy (SEM). After 60 curing days the main phases present in the TTK-cement system were the CSH gel, Gehlenite Hydrated Amorphous (C2 ASH8 ) and Portlandite (CH). The kaolin treatment temperature affects the hydrated system phase composition.