Calcium aluminate cements [CACs] are typically used for cast-in-place structural work and high temperature applications due to their unique properties. The CaAl₂O₄ [CA] and Sm-doped CaAl₂O₄ [CA:Sm] cement clinkers obtained by the solid-state reaction were investigated using X-ray powder diffraction [XRD], scanning electron microscopy [SEM] and energy dispersive X-ray spectroscopy [EDS] and luminescence spectroscopy. The XRD result shows that the powders are pure CaAl₂O₄. As a next step, hydration behavior of as-synthesized cements was investigated by both classical methods including isothermal calorimetry and XRD, and the state-of-the-art techniques including time resolved electrochemical impedance spectroscopy [TR-EIS] and luminescence spectroscopy. The TR-EIS investigations were obtained by the Impedance Camera over the range of 100 Hz to 1 MHz frequencies. The evolution of obtained EIS and luminescence spectra easily manifested the beginning of the new solid formation and the hydration kinetics. The dynamics of hydration processes were also successfully traced by the changes of the luminescence intensity from the Sm³⁺ ions. This technique seems to be complementary, and consistent with other methods implemented in the cement chemistry, especially to investigate e.g. hydration of ordinary Portland cements [OPCs] and other binders.