TlxS layers of different composition on the surface of polyethylene are formated at first by sulfuration of PE in a solution of higher polythionic acid (H2S33O6) and then by treating it with alkalified up to pH 11,4 thallium(I) sulphate solution. Depending on the conditions of sulfuration and treatment with Tl(I) salt solution, red brownish or grey brown TlxS layers in the surface matrix of PE having different composition were obtained. A kinetic study showed that the amount of thallium in the sulphide layer increased with increasing the duration of PE sulfuration, the temperature of polythionic acid solution, time of sulfured PE treament in the solution of Tl2SO4 and the temperature of this solution. The stoichiometrical composition of layers according the data of chemical analysis varies from Tl0.3S to Tl2.5S. A phase composition of the layers obtained studied by the methods of X-ray photoelectron spectroscopy and X-ray diffraction. The data of Tl 4f7/2, O 1s and S 2p spectra showed that thallium is bonded with sulfur into TlS and Tl2S, but the Tl2SO4 and Tl(OH)3 are adsorbed on the layers surface too. Five thallium sulfide phases, TlS, Tl2S, Tl2S2, Tl4S3 and Tl2S5 were identified in the composition of the layers by X-ray diffraction but the maxima of TlS phase predominates in the diffractograms.The morphology of the TlxS layers during formation and growth was investigated by Atomic Force Microscopy.