Impedance spectroscopy was used to monitor the hydration in the electrical/dielectric behaviors of chemical mechanical planarization (CMP)-blended cement mixtures. The electrical responses were analyzed using their equivalent circuit models, leading to the separation of the bulk and electrode based responses. The role of the CMP slurry was monitored as a function of the relative compositions of the CMP-blended cements, i.e. water, CMP slurry, and ordinary Portland cement. The presence of $Al_2O_3$ nanocrystals in the CMP slurries appeared to accelerate the hydration process, along with a more tortuous microstructure in the hydration, with enhanced hydration products. The frequency-dependent impedance spectroscopy was proven to be a highly efficient approach for evaluating the electrical/dielectric monitoring of the change in the pore structure evolution that occurs in CMP-blended cements.