AbstractThe adsorption and self‐organisation process of alkyl‐phosphonic acids and phosphoric acid monoalkyl esters on technical aluminium surfaces have been investigated by different surface sensible techniques: Grazing angle FT‐IR‐ spectroscopy, angle dependent XPS and Auger‐ spectroscopy. The aim of these studies was to replace the present technical procedure for pretreatment of aluminum surfaces with Chromate acid in order to improve the corrosion inhibition and the coating adhesion.The ability for self‐assembly is given by substances which have a surface reactive group and a long‐aliphatic or aromatic spacer and a supramolecular order is built‐up between these spacers. The results show that these molecules are able to adsorb spontaneously onto the aluminum surface and subsequently a structured molecular order is formed.These effects were confirmed by industrial linked adhesion and