To elucidate the role of chemical interactions in the promotion of metal–polymer adhesion, a poly(ethylene terephalate)/copper system was studied. Surface photografting of unsaturated monomers containing different chemical functional groups onto a three‐mil poly(ethylene terephthalate) film provided a means of examining a variety of copper‐polymer interfaces. Initial graft verification was accomplished via contact angle measurements. Adhesion strengths to vacuum‐deposited copper were determined using 90° peel tests. Graft analysis, as well as investigation of the interfacial interaction between copper and the grafted moieties, was accomplished using X‐ray photoelectron spectroscopy. Copyright © 1989 John Wiley & Sons, Inc.