The interest in self-assembling monolayer deposition on various, oxide substrate surfaces is steeply increasing in the last decades. Although many studies are being performed, literature does not come with a general insight in the adsorption of these layers on oxide surfaces. Also for the deposition of phosphonic acids on aluminum oxides, there is no global consensus. In this paper, we present an original in situ analysis in order to eludicate the real layer formation mechanism, First of all, the state of the phosphonic acid molecules was determined using DOSY NMR, making sure that no structures other than, free molecules were present at the concentration used. With in situ atomic force microscopy and in situ visual ellipsometry, multilayers of phosphonic adds, showing 3D island growth, were determined. It was shown that using, the variation of the in situ obtained roughness and bearing ratio, together with the equivalent thickness modeled by ellipsometry, the growth of the layers occurs in situ in three different stages. They consist of increasing number of islands growth, followed by filling up the gaps between islands. At last, within the adsorption time frame measured, the islands grow further in dimensions but not in numbers. This closely corresponds with the behavior of the octylphosphonic add films analyzed by ex situ techniques.