Aluminum based surfaces are routinely coated with a chromate based layer that provides unparalleled corrosion protection. Widely used conversion coating treatment formulations contain hexafluorozirconate as a major constituent besides chromate, ferricyanide, fluoride, and fluoborate. The function of hexafluorozirconate is the subject of this study as its function is still largely unknown. Hydrophobicity, surface morphology, and the chemistry of the surface, resulting from treatment with hexafluorozirconate, were studied using contact angle measurements, scanning electron microscopy, and energy dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy was extensively utilized to determine the chemistry of the surface resulting from the hexafluorozirconate pretreatment. Our results indicate that fluoride ion containing hexafluorozirconate complex does not attack the oxide film in a manner that uncomplexed simple fluoride ion does. Hexafluorozirconate is involved in the formation of an Al-Zr-O-F based hydrated layer that increases the hydrophilicity of the surface, activates the surface, and lowers the corrosion resistance. These factors enhance the interaction of chromate with the alloy surface to result in the formation of a uniform conversion coating. Based on these results, a new model has been proposed for the formation of chromate conversion coatings. (c) 2005 Elsevier Ltd. All rights reserved.