Poly(ethylene) (PE) films were treated with a carbon dioxide (CO2) plasma to study the formation of oxygen-containing functional groups at the surface. Modified and nonmodified films were characterized by X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. During the CO2 plasma treatment, the PE surface is etched and oxidized, yielding films with a very hydrophilic surface. The oxygen incorporation at the surface is fast and can be described by a combination of a zero-order incorporation and a first-order etching process. Several oxygen functionalities such as carboxylic acid (approximately 14% of the oxygen present), ketone/aldehyde (25%), and hydroxyl/epoxide (5-9%) groups were introduced at the surface by the plasma treatment. This was shown by using derivatization reactions for specific functional groups followed by XPS analysis. The wettability of the plasma-treated surfaces decreased when the films were stored for prolonged periods of time in air. This aging process could not be completely reversed by immersion of the films in water.