The structure of thefilm formed by oleylpropanedi-amine (OLDA) on the copper (Cu) metal surface in water at 150 degrees C was investigated by combining quantitative NMR and surfacecharacterization methods. We succeeded in quantifying the amountoffilm formation by precisely determining all mass balances in thesystems examined. 2D IR microscopic mapping showed that thefilm thickness is uneven in the horizontal direction with a lengthscale of similar to 100 mu m and hundreds of OLDA layers. Thisfilmthickness was also confirmed by AFM. The analysis of the C-Hstretching vibrational frequency disclosed that the alkyl chains arehighly ordered in the layers close to the Cu surface and areconformationally disordered in the layers distant from the Cusurface in the thicker portion of thefilm. Combining XPS measurements using argon gas cluster ion beam etching with the ICP-AESanalysis, we revealed that the key to multiple layering is the formation of a coordination complex of the unprotonated amino groupsof OLDA with Cu that presumably results in polymer chain-like network structures. Contact angle measurements at different OLDAconcentrations and treatment times showed that the water repellency of thefilm originated from the thick layering of OLDAmolecules with disordered hydrophobic chains.