Performances of hot-dip galvanized coatings not only depend on composition of the bath or the coating but significantly on the structure too. Nickel has been reported to have significant role in the improvement of the process but there is lack of sufficient reported detailed evidences. As it has already been reported that a nickel-rich barrier layer is formed during galvanization, and that the layer efficiently suppresses pitting, the present study focuses on investigating the role of nickel on the performance of hot-dip zinc coating. The structural influence due to the presence of nickel in galvanized substrates is discussed in this paper. Influence of nickel-rich barrier layer is identified as the cause for substantial improvement of the coating performance. Nickel content in the galvanic coating was analyzed layer-by-layer. Different techniques like OCP measurement and anodic polarizations were adopted to investigate and study the correlation between the structural change and the galvanic performance of the coating. The formation of nickel-rich barrier inner layer has a key role in improving the galvanic performance of the coating. © 2004 Elsevier B.V. All rights reserved.