Interfacial reactions of polyimide with several metals have been investigated by XPS and TEM to determine their effects on adhesion and long term stability. It has been found that the polyimide-on-metal interface and the metal-on-polyimide interface are intrinsically different; in the case of PI-on-metal interface, the precursor of polyimide, polyamic acid, reacts with the metal resulting in a strong chemical bond and therefore, higher adhesion strength than the corresponding metal-on-PI interface. Both interfaces are found susceptible to T/H environment, resulting in significant adhesion loss. The mechanical and electrical properties of polyimide may be altered as a result of the interaction with metals and therefore, great care is necessary to insure a stable interface and the reliability of devices.