In the present work, an industrial polyester coil-coated steel was characterized by electrochemical impedance spectroscopy (EIS) during immersion in a 0.5 M NaCl solution for different temperatures (30, 40, 50 and 60 °C). The objective was to propose a methodology to follow the ageing of the coil-coated system, from the first stage of water uptake until the blistering appearance. Relevant parameters were extracted from the EIS diagrams to analyse ageing processes of the polymer and of the metal/polymer interface. Water uptake was determined from the high-frequency part of the impedance diagrams using a linear rule of mixtures. By increasing the temperature, both the water uptake kinetics and the water content in the coating increased. The effect of water uptake on the physical structure of the coating (plasticization) was discussed through the analysis of a time constant corresponding to the dielectric manifestation of the polymer glass transition. At 40, 50 and 60 °C, appearance of corrosion was detected on the impedance spectra by a decrease, at low frequency, of the impedance modulus and of the phase angle. For 60 °C, the corroded surface area as a function of time, was assessed from the EIS data analysis with adapted equivalent circuits. The corroded surface areas followed similar trend as blister surface areas determined from images analysis.