The effect of topcoat properties on the tendency of painted materials to blistering was studied. Six topcoats were applied on identical panels of hot-dip galvanized steel painted with a polyester primer. The tendency to blistering was assessed under the conditions of permanent condensation in a Q-panel condensation test at 60 °C. Internal tensile stress and stress development in organic coatings during temperature and relative humidity cycling were investigated by the cantilever curvature method. Although blisters originated from the metal/polymer interface, the extent of blistering was strongly influenced by the topcoat. Available data suggest that it may increase with the coating thickness, glass transition temperature (Tg) and thermal expansion properties. Connection was found between the internal tensile stress formed in topcoats during the paint film preparation and the extent of blistering. A hypothesis that stress-assisted interfacial bond hydrolysis was responsible for blister initiation is proposed. Other experiments suggested that local paint buckling over non-adherent sites can be caused by plastic deformation of the paint due to relief of compressive stress generated at elevated temperature or by ingress of water.