A combination of surface spectroscopy and microanalytical techniques have been used to investigate the chemical and material characteristics of interfaces formed between metal and a high temperature polymer, polyimide. Results reveal significant chemical reactivity at the interface, as manifested by intermixing and cluster formation. The extent of the material reaction is strongly influenced by the bonding characteristics between metal and the polyimide. Results on Cu and Al are reviewed to illustrate the chemical trend due to increasing reactivity.