This paper reports the investigations on the early hydration process of fresh concrete using a non-contact electrical resistivity measurement. The bulk resistivity development (
ρ(
t)–
t curves) and the pore solution resistivity development (
ρ0(
t)–
t curves) of fresh concrete, with and without fly ash replacement, were obtained for the period from casting to the age of 48 h. The porosity development (
(
t)–
t curves) was obtained from the
ρ(
t)–
t and
ρ0(
t)–
t evolution curves with the calculated initial porosity and the measured porosity at 1 day by mercury intrusion porosimetry (MIP). The degree of hydration (
α(
t)–
t) of the cement-based materials was then obtained based on the porosity change with time, which was caused by the increase of hydration products with a lower density as compared to that of the original cement in the hydration system. The comparison of the degree of hydration predicted from the porosities (
(
t)–
t) and obtained from the experimental measurement of non-evaporable water showed a good agreement of the two.
The setting and hardening behavior of fresh concrete was characterized by the characteristic points on the ρ(t)–t and dρ(t)/dt–t curves. The retarded hydration caused by the fly ash incorporation could be identified by the characteristic points.