The investigation of etching and sputtering processes at polymer surfaces, especially PTFE, caused by 1–10 keV ions led to interesting results. At the target surface a characteristic "fibre-like" microstructure of quasicrystallites is developed, and the sputter yields of this selective surface etching are unusual high (≈102 CF2-groups per incident ion). Films deposited from these fragments with ion beam sputtering under high vacuum conditions are transparent, they possess a (100)-quasicrystalline orientation and a low friction coefficient.