Zeta potential according to the hydration time was studied during the early hydration of C3S with and without CO2 atmosphere. Zeta potential was low as a level of 20mV at the first and second exothermic peaks of heat evolution, but it was rapidly increased up to a level of 300mV. In the CO2 atmosphere, zeta potential was level of 60mV at 10 minutes hydration and it's value became a low gradually according to the hydration time. Zeta potential was also proportioned to the Ca2+ concentration in the liquid phase, i.e., there was positive correlation between zeta potential and Ca2+ concentration. The existence of silicate layer was not found out on the hydrated C3S in the CO2 atmosphere by SEM-EDAX.