In order to introduce carboxylic acid groups at the surface of poly(ethylene) (PE) films, an attempt was made to covalently link a preadsorbed layer of poly(acrylic acid) (PAAc) on a PE film by an argon or tetrafluoromethane (CF4) plasma treatment. Surface analysis was performed by XPS (X-ray photoelectron spectroscopy) and water contact angle measurements. It was shown that by treatment of a PAAc layer preadsorbed on PE with an argon or a CF4 plasma, a small amount of carboxylic acid groups was introduced at the surface. A similar amount of these groups was obtained by plasma treatment of PE films without a preadsorbed PAAc layer. A comparison of the etching rates of PAAc and PE by either an argon or a CF4 plasma, showed that PAAc is etched much faster by both types of plasmas than PE. The preadsorbed PAAc layer on PE is etched off before it could be immobilized by either an argon or a CF4 plasma treatment. Additionally the effect of treating PE films for very short times with an argon or a CF4 plasma was studied. After an induction period of approximately 0.1 s, the oxidation during the argon plasma treatment and the fluorination during the CF4 plasma treatment were proportional to the logarithm of the treatment time for time periods up to 50 s.