Corrosion protection is commonly achieved by applying a thin polymer coating on the metal surface. Many studies have been devoted to local events occurring at the metal surface leading to local or general corrosion. In contrast, changes occurring in the organic coating after exposure to corrosive conditions are much less studied. In this article we outline how changes in the coating itself due to curing conditions, environmental and erosion effects can be investigated at the nanometer scale, and discuss how such changes would affect its corrosion protection performance. We focus on a waterborne hydroxyacrylic-melamine coating, showing high corrosion protection performance for carbon steel during long-term (≈35 days) exposure to 0.1 M NaCl solution. The effect of curing time on the conversion of the crosslinking reaction within the coating was evaluated by fourier transform infrared spectroscopy (FTIR); the wetting properties of the cured films were investigated by contact angle measurement, and the corrosion resistance was studied by electrochemical impedance spectroscopy (EIS). In particular, coating nanomechanical and wear properties before and after exposure to 0.1 M NaCl, were evaluated by atomic force microscopy (AFM). Fiber-like surface features were observed after exposure, which are suggested to arise due to diffusion of monomers or low molecular weight polymers to the surface. This may give rise to local weakening of the coating, leading to local corrosion after even longer exposure times. We also find a direct correlation between the stick-slip spacing during shearing and plastic deformation induced in the surface layer, giving rise to topographical ripple structures on the nanometer length scale.