X-ray photoelectron spectroscopy (XPS) is used to analyse variations during exposure to humidity and UV radiation (UVCON test) in the chemical composition of the outer surface of organic coatings (lacquers) containing phosphating or chromating reagents applied on galvanised steel, galvanneal and galfan substrates. By means of electrochemical impedance spectroscopy (EIS) measurements the protective character of the coatings analysed by XPS is studied and an attempt is made to establish possible relationships between the chemical composition of the surface of the lacquered substrates after exposure to the UVCON test and their electrochemical characterisation in immersion in a 3% NaCl solution. In general, the formation of defects or the loss of adhesion of the lacquer film leads to a significant reduction in charge transfer resistance values and, at the same time, an increase in interfacial capacitance values. The special behaviour of the galfan/lacquer "with chromating reagents" system is associated with the presence of a thin insulating film of chromium and aluminium oxides at the base of the pores in the lacquer. Interfacial capacitance values tend to evolve in close correspondence with the content of some elements on the surface of the materials. (C) 2003 Elsevier Ltd. All rights reserved.