The electrochemical response of a soft magnetic FeNbAlMnCuSiB alloy was studied through different stages of devitrification. The structural evolution including appearance of a nanocrystalline phase and intermetallics, and accompanying surface topographical changes were studied and correlated to the electrochemical behavior of this alloy. The electrochemical behavior was not directly related to changes in surface roughness but it was very responsive to the structural changes, particularly to the formation of the nanocrystalline phase and to the precipitation of Fe 7Nb 6 phase. There was a progressive passivation breakdown with the appearance of crystalline phases on annealing. © 2005 Springer Science + Business Media, Inc.