Surface modification of H-2 plasma-pretreated poly(tetrafluoroethylene) (PTFE) films, either by plasma polymerization and deposition of GMA, or by UV-induced graft copolymerization with glycidyl methacrylate (GMA), was carried out for adhesion enhancement with the electrolessly-deposited copper. XPS and FTIR results revealed that the epoxide groups in the plasma-polymerized CMA (pp-GMA) layer had been preserved to various extents, depending on the glow discharge conditions. The T-peel adhesion test results showed that the adhesion strengths of the electrolessly-deposited copper on both the pp-GMA modified PTFE (pp-GMA-PTFE) film and the CMA graft-copolymerized PTFE (GMA-g-PTFE) film were much higher than that of the electrolessly-deposited copper on the pristine or the H-2 plasma-treated PTFE film. The high adhesion strength between the electrolessly-deposited copper and the surface-modified PTFE film was attributed to the fact that the plasma-polymerized and the UV graft-copolymerized GMA chains were covalently tethered on the H-2 plasma-pretreated PTFE surface, as well as the fact that these GMA chains were spatially and interactively distributed into the copper matrix.