The surface properties of polystyrene as a possible catalytic support for active coordinative species were investigated. To improve the surface properties, discharge treatments in the presence of oxygen and ammonia were carried out. The polymer surface was studied before and after the plasma treatments. Contact angles for the polymer surface were measured in order to determine the surface free energy. Polymer-bound complex catalysts were prepared by anchoring PdCl2 on the surface of the polystyrene samples. The chemical compositions were studied by X-ray Photoelectron Spectroscopy (XPS). Plasma treatments in the presence of oxygen or ammonia caused an increase in the surface free energy of polystyrene, as a consequence of the higher concentration of oxygenated or nitrogenated functional groups, respectively, on the polymer surface. Contact angle measurements are in agreement with the corresponding values obtained by XPS. After treatment with PdCl2, the amount of palladium anchored to the polymer surface treated with ammonia is greater than in the case of the oxygen plasma treatments; this may be explained on the basis of the higher nucleophilic character of the amine groups. No palladium was detected in the untreated polystyrene surface.