Surface modification of poly(tetrafluoroethylene) (PTFE) film by H-2 plasma treatment, and by plasma polymerization and deposition of glycidyl methacrylate (GMA) in the absence and presence of H-2 plasma pre-activation of the PTFE substrates, was carried out to enhance the adhesion of the polymer with evaporated copper. The H-2 plasma treatment resulted in effective defluorination and hydrogenation of the PTFE surface, and enhanced the adhesion of evaporate Cu to the PTFE surface (the Cu/PTFE assembly) to various extents. For plasma polymerization carried out at a low RF power, a high epoxide concentration was preserved in the plasma-polymerized GMA (pp-GMA) layer on the PTFE surface (the pp-GMA-PTFE surface). However, high adhesion strength for the Cu/pp-GMA-PTFE assembly was obtained only in the presence of H-2 plasma pre-activation of the PTFE substrates prior to the plasma polymerization and deposition of GMA. In the absence of H-2 plasma pre-activation, the deposited pp-GMA layer on the PTFE surface could be readily removed by acetone extraction. The adhesion enhancement of the Cu/pp-GMA-PTFE assembly in the presence of H-2 plasma pre-activation of the PTFE substrate was attributed to the covalent bonding of the pp-GMA layer with the PTFE surface, the preservation of the epoxide functional groups in the pp-GMA layer, and the strong interaction of evaporated Cu atoms with the epoxide and carboxyl groups of the GMA chains.