Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow-discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma-polymerized GMA (pp-GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp-GMA film with well-preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T-peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp-GMA-modified PTFE (pp-GMA-PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma-treated PTFE film.