Impedance Spectroscopy (IS) has been used to study microstructure and hydration mechanism of cement pastes. In this work, the early hydration behaviour of portland cement paste with different blame values and contents of blast-furnace slag was investigated by IS. As slag was added to portland cement, the values of $R_{t(s+1)}$ (the solid-liquid phase resistance) and $R_{t(int)}$ were decreased in the early hydration period. It showed that hydration of cement paste containing slag was slower than it of the reference cement paste. As the content of slag was increased, the values of $R_{t(s+1)}$ was decreased. Furthermore, the diameter of semicircle, $R_{t(int)}$ observed at 72 hours was decreased with the increment of slag content. However, the values of $R_{t(s+1)}$ and $R_{t(int)}$ were increased with blame value of slag from the early hydration period.