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Abstract: Layered nanocomposite PEG/WS2, intercalating oligomeric poly(ethylene glycol) (PEG6000) into the tungsten disulfide host galleries, was synthesized using the exfoliation-adsorption technique. X-ray diffraction revealed that the intercalated oligomer within the host galleries is in a double-layer arrangement with an interlayer expansion of about 8.8Å. The optimum conditions were explored to prepare the single-phase product with a composition of Li0.12(PEG)1.51WS2. Thermal analyses suggested that the resulting material shows good thermal stability, with the decomposition of the interacted oligomeric chains within the disulfide galleries occurring at around 258°C. Despite high conductivity of the host material, those of the PEG/WS2 nanocomposite were found to be high in the order of 1×10−2 Scm−1 at ambient temperature, resulted from the host guest–host charge transfers. [Copyright &y& Elsevier]