The behavior of CaO and SiO2 in the reaction produced which produced in the early hydration of C3S was studied by XRD and thermal analyzer. Polymerization of hydrated siltcates was also studied by TMS method. TMS derivatives were separated by gaschromatography. Cao/SiO2 molar ratios of the produced CSH gel under the air atmosphere were higher than that in the CO2. Dimerization rate of hydrated silicates was very fast in the early hydration stage. Trimer began to appear later than dimer and its increasing rate was very low. The amount of dimer and trimer formed under the CO2 atmosphere was less than that in the air.