The effect of thickness, curing temperature and solvent on the structural inhomogeneity of several types of organic coatings has been investigated. The local distribution of electrochemical resistance was studied using a wire beam multielectrode array, while the inhomogeneity at a larger scale was examined using ∼3 cm2 area detached coatings. Physicomechanical tests were also employed to address the structural changes occurring because of variation in curing temperature and the type (or absence) of solvent. Results acquired by wire beam electrode and from the detached coatings showed that increasing the thickness and curing temperature improves the homogeneity of the coating as does elimination of solvent. Waterborne coatings exhibited a relatively homogeneous low resistance with a resistance lower than the threshold required for effective corrosion protection. Results of physicomechanical examination suggest that unreacted functional groups and water absorption are of the main causes of formation of structural defects in organic coatings.