Sulfate groups were introduced at the surface of poly(ethylene) (PE) samples. This was accomplished by immobilizing a precoated layer of either sodium 10-undecene sulfate (S11(:)) or sodium dodecane sulfate (SDS) on the polymeric surface by means of an argon plasma treatment. For this purpose, S11(:) was synthesized by sulfating 10-undecene-1-ol using the pyridine-SO3 complex. The presence of sulfate groups at the polymeric surfaces was confirmed by X-ray Photoelectron Spectroscopy (XPS). The presence of an unsaturated bond in the alkyl chain of the surfactant improved the efficiency of the immobilization process. About 25% of the initial amount of sulfate groups in the precoated S11(:) layer was retained at the PE surface compared to only 6% for SDS. The maximum surface density of sulfate groups on the resulting samples was one group per 45 and 127 Angstrom(2) respectively.