The understanding of the molecular aspects of adhesion needs the determination of the molecular order of macromolecular chains at the polymer/metal interface. Thin supported polymer films are studied by FTIR reflectance analysis (IRRAS). It is shown that the development of specific acid-base interactions at the interface is able to strongly organize and order macromolecular chains at the vicinity of the interface. Microstructural parameters of the polymer are shown to influence both interfacial organization and adhesion.