The degradation process of a red iron oxide epoxy coating on three kinds of metals under a periodic cycling exposure to 3.5 wt% NaCl solution (45 °C 12 h + 25 °C 12 h) was comparatively studied using electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) methods. The influence of the metal substrates (carbon steel, brass, and Al alloy) on the protection performance of the coating was analyzed using variations in the electrochemical and chemical parameters. The failure criteria of the coating were discussed. The results show that the coating on the three substrates presents different failure times, with the coating on steel presenting the shortest time and the coating on Al alloy the longest time. The characteristics of metal substrates and their corrosion products influence the coating failure behavior. The corrosion products with loose and hygroscopic properties of steel and brass have promoting effects on the diffusion of water through the coating. The passive film of the Al alloy substrate and the formation of salt film containing Cl- have corrosion-inhibiting effects on the substrate. Evaluation of the coating performance by |Z|0.01Hz should consider the characteristics of the metal substrates.