X-ray photoelectron spectroscopy (XPS) has been used to study the chemical effects of both inert (argon) and reactive (oxygen, nitrogen, and mixed gas) plasma treatments done in situ on a variety of polymer surfaces. Inert gas plasma treatments introduce no new detectable chemical species onto the polymer surface but can induce degradation and rearrangement of the polymer surface. However, plasma treatments with reactive gases create new chemical species which drastically alter the chemical reactivity of the polymer surface. These studies have also shown that the surface population of chemical species formed after plasma treatment is dependent on both the chemical structure of the polymer and the plasma gas. The effects of direct and radiative energy-transfer processes in a plasma have also been studied. Polymers containing certain functional groups were found to be more susceptible to damage via radiative energy transfer. Ageing studies of plasma-modified polymer surfaces exposed to the atmosphere have shown that the ageing process consists of two distinct phases. The initial phase, which occurs rapidly, involves adsorption of atmospheric contaminants and, in some cases, specific chemical reactions. The second phase, which occurs slowly, is due to surface reorganization.