The dielectric permittivity of cementitious materials during 24 hours hydration period at a frequency of 2.45 GHz using a network analyzer with open-ended probe technique was measured. Influences of water-to-cementitious ratios, cement types, pozzolans and aggregate types are taken into consideration. The results show that dielectric permittivity is strongly affected by initial water-to-cementitious ratio and the rate of hydration reaction which can be changed by fineness of cement (Types 1 and 3), pozzolan materials and aggregates (river sand with/without crushed limestone rock). Dielectric permittivity is relatively high and remains constant during the dormant period, after that it decreases rapidly when the hydration reaction resumes and continues to decrease during the acceleratory period.