This study uses confocal microscopy and image processing to investigate the microstructural changes of coating–metal systems immersed in a heated acidic bath. Unlike standard optical microscopy techniques, 3D confocal microscopy images can quantitatively reveal microscopic defects formed at early stages of cathodic delamination. The coatings are made of fluorescent epoxy–phenolic resins cured at high temperatures onto tinplate (T23) and tin-free steel (TFS) substrates. When the coated metal substrates are immersed in acetic acid, a series of microscopic corrosion events occur at the polymer–metal interface. These events are quantified by changes in the thickness distribution of the degraded samples relative to that of intact coatings. The degradation rate is highest for epoxy–phenolic polymers on TFS substrates, represented by multiple orders of magnitude increase in the number density of defect sites. Higher molecular weight coatings provide slightly better resistance against delamination. The coating thickness dictates the rate of oxygen diffusion and ion transport along the polymer–coating interface, where raised asperities serve as localized sites for metal oxidation and formation of alkaline species, leading to subsequent delamination of the cured polymers from the surfaces. The results show that the metal surface topology is as important as chemistry when designing the corrosion resistance of products containing acidic liquids, and that confocal microscopy is useful in quality control through early detection of mesoscale polymer failure.