Impedance spectroscopy was applied to the initial hydration of calcium phosphate bone cements in order to investigate the electrical/dielectric properties. Hydration or equivalently setting was monitored as a function of the amount of water and initial powder characteristics. Higher amounts of water produced more open microstructures, leading to higher conductivity and enhanced dielectric constant. The effects of the initial characteristics in the powder were investigated using bone cement powder prepared with and without granulation. Granulated powder exhibited a significant change in resistance and produced a higher dielectric constant than those of conventional powder. Through a simplified modeling, the effects of thickness in reaction products and pore sizes were estimated by the frequency-dependent impedance measurements. Furthermore, impedance spectroscopy was proven to be a highly reliable tool for evaluating the continuous change in pore structure occurring in calcium phosphate bone cements.