The film formation process in waterborne (WB) epoxy coatings is studied using electrochemical impedance spectroscopy (EIS) measurements and dynamic mechanical analysis (DMA). Ten epoxy coatings with different pigment volume concentration were prepared on standard steel substrates and carefully monitored over four weeks (30 days). It is shown that impedance spectroscopy can serve as a very sensitive tool for accurate experimental detection of the critical pigment volume concentration. We also show that the optimal film formation process and corrosion stability of coatings are greatly affected by the coating pigment volume concentration (PVC) value. As a whole, the study confirms that the optimization of coating protection ability needs to take into account both maximization of the barrier effect as well as maximization of the degree of epoxy-amino cross-linking.