AbstractThe surface characteristics and corrosion behaviour of the AZ31 magnesium alloy exposed to a high relative humidity (RH) atmosphere were investigated. During the first 15 days of humidity test at 98% RH and 50 °C, a significant increase of magnesium carbonate and a decrease of magnesium oxide were detected on the surface film by XPS; after this stage, increased exposure times did not produce substantial changes on the relative amounts of these compounds. The surface film of commercially pure magnesium, also examined for comparison purposes, revealed more magnesium carbonate and less magnesium oxide compared with the AZ31 alloy. Unlike the AZ31 alloy, the surface of pure Mg disclosed almost complete substitution of MgO by magnesium carbonate after 30 days of exposure time. Mass gain values of tested specimens and scanning electron microscope characterisation of corroded surfaces indicated lower corrosion susceptibility of the AZ31 alloy compared with the commercially pure Mg, suggesting superior chemical stability of the oxide/hydroxide film formed over the magnesium–aluminium alloy surface. XPS and energy dispersive X‐ray (EDX) analyses did not revealed any substantial enrichment of aluminium in the corrosion products film on the AZ31 alloy after 30 days of testing. Copyright © 2008 John Wiley & Sons, Ltd.