Ultra-thin films of polyamic acid (BTDA-ODA type) are prepared by spin coating a very dilute solution onto bare or metallized silicon wafers (estimated thickness 25 ± 5 Å). The XPS analysis of the various polymer/metal interfaces suggests the occurrence of acid-base type interaction between the carboxylic groups of the polymer and the oxides and hydroxides that cover the Ni and Cr surfaces. When these systems are in situ cured, the XPS analysis shows the occurrence of a variety of chemical interfacial reactions. In particular: (i) when the substrate is a naturally passivated Ni layer, the complete destruction of the polymer is observed; (ii) when the substrate is a naturally passivated Si wafer, no relevant interaction occurs; (iii) for a naturally passivated Cr and an oxidized Ni surface, partial decomposition of the polymer is observed. The above effects are explained in terms of the acid or basic properties of the oxidized layers that cover the metal surfaces, and in terms of their stability toward heating.