The changes of electrical resistivity with time of cement pastes with water to cement ratio of 0.23, 0.35 and 0.53 were in situ continuously monitored by using electrodeless resistivity apparatus. Isothermal conduction calorimeter was also used to measure the hydration degree. The quantitative relationship between electrical resistivity evolution of paste and development of pore structure was proposed during hydration process. The results show that four stages (dissolution, induction, acceleration and deceleration) are identified according to the characteristics of electrical resistivity and its differential resistivity curves. In addition, a lower water to cement ratio shows a smaller capillary porosity and constriction factor as well as a higher tortuosity factor, resulting in a higher electrical resistivity of bulk paste, and the reverse phenomenon is observed with the electrical resistivity of pore solution.