The electrical properties of fly ash, slag and limestone powder-cement paste were studied by the methods of Cyclic Voltammetry and AC Impedance Spectroscopy. The results of electrical test were fitted by equivalent circuit. The correlations between electrical parameters of paste and unevaporable water content, pore structure by mercury porosimetry were compared. The results show that there is a positive relation between the unevaporable water content and the electrical resistivity of paste. If the unevaporable water content is higher, the hydration degree is higher and the electrical resistivity of paste is higher. The electrical resistivity of paste is increased with fly ash and slag, and it is unaffected with limestone powder of 5% dosage. The resistance Rs of pore solution of paste is increased with the prolongation of hydration, and the changes of resistance Rs and the electrical resistivity are unanimous. The resistance Rp and electrical capacitance C of gel are related to C-S-H content, and there is a negative relation between the resistance Rp and electrical capacitance C of gel. The complexity of pore structure of paste is increased with the prolongation of hydration. The constant phase angle exponent P by AC Impedance Spectroscopy is decreased and the value of fractal dimension by mercury porosimetry is increased.