The effect of Al on the galvanic ability of Zn-Al coating has been Studied under thin electrolyte layers by measuring surface potential and surface pH. The changes of surface potential and surface pH over Zn-Al/steel galvanic couple corroding in artificial sea water (ASW) were measured at 60% and 90% RH at 298 K. In the initial stage of corrosion, Zn-55Al coating has shown better galvanic protection ability than Zn-5Al coating in both 60% and 90% RH. However, Zn-5Al coating was better in long term corrosion. The better galvanic ability of Zn-55Al coating in the initial stage of corrosion was related to the observation of pH as low as low as 2 on its Surface. The low pH value was due to hydrolysis of Zn2+ and Al3+ ions. The low pH value was further confirmed by observing evolution of gas due to H+ reduction on the Zn-55Al coating. With the progress of corrosion, the low pH region of coating layer extended towards the base steel. This helped expand the deposition of zinc corrosion products on the steel surface. The enhanced dissolution of zinc in Zn-55Al coating led to the formation of a barrier layer which limited the galvanic protection of remaining steel. This was not the case in Zn and Zn-5Al coating. The X-ray analyses of the corroded samples have shown the deposition of zinc corrosion products on the steel surface, which greatly depended on the RH value. The part of the steel surface covered with zinc corrosion products has shown relatively less noble potential than other part indicating that zinc corrosion products took a role to protect the base steel against corrosion. The results from surface potential and surface pH measurements were substantiated by the surface observation of the corroded sample during and after the corrosion test. (c) 2006 Elsevier Ltd. All rights reserved.