Surface modification with self-assembled alkyl-phosphonic acid layers is a powerful technique for corrosion protection of different metals. In the present study, passivated, native (covered with air-formed oxide) and metallic iron surfaces were used as substrates. The influence of the oxide on the phosphonate layer formation; the corrosion protective effect of the phosphonate layer and the structure of the modified surfaces were investigated. The layer formation process was monitored directly in the phosphonate-containing solution. it was found that the phosphonate layer formation process depends on the conditions applied during iron passivation, and the oxide layer has an important role in the stability of the protective layer, while the bare metallic iron surface is disadvantageous for phosphonate bonding. Conversion electron Mossbauer spectroscopy (CEMS) and X-ray photoelectron spectroscopy (XPS) proved the presence of phosphonate layer on the top of the passive iron surface, with the thickness around monolayer. (C) 2009 Elsevier Ltd. All rights reserved.