In the past, nondestructive techniques, which were used exclusively for structural inspection, have been used to assess the properties of early-age concrete recently. The setting time indicates the time of the form removal and the initial onset of the strength. The setting time is based on the hydration of cement. These setting time assessment techniques are representative of the Vicat needle test and the penetration resistance test, which are difficult to measure for structures and are requiring wet-sieving of concrete sample. Recently, several nondestructive techniques, such as ultrasonic pulse velocity measurement, hydration heat measurement and electrical impedance measurement, are proposed to evaluation the setting time of cement-based materials. This study aims to measure electrical resistivity in order to monitor microstructural evolution. For this purpose, an optimized experimental setup is proposed by performing a series of pre-test analyses. A total of 37 cement-based material mixes are prepared to study the effects of the use of various chemical admixtures, various curing environmental condition, and various mix-proportions. As a result, three parameters, such as the initial electrical resistivity, the rising time and the increasing ratio of electrical resistivity, are proposed to reflect a microstructure development by hydration of cement-based materials. All parameters are discussed with conventional test results obtained from the penetration resistance test and the ultrasonic pulse velocity measurement. The correlation between electrical parameters and the setting time of penetration resistance test are shown, and the proposed equations is used to indicate the initial setting time and the final setting time in the penetration resistance test.