Abstract Conductive polymer/sulfur composite materials were prepared by heating the mixture of polyacrylonitrile (PAN) and sublimed sulfur. During the heating process, PAN was dehydrogenated by sulfur, forming a conductive main chain similar to polyacetylene. At the same time, the high‐polarity functional group –CN cyclized at the melt state, forming a thermally stable heterocyclic compound in which sulfur was embedded. The nanodispersed composites showed excellent electrochemical properties. Tested as cathode material in a non‐aqueous lithium cell based on poly(vinylidene fluoride) (PVDF) gel electrolyte at room temperature, the composite exhibited a specific capacity up to 850 mA h g –1 in the initial cycle. Its specific capacity remained above 600 mA h g –1 after 50 cycles, about five times that of LiCoO 2 , and recovered partly after replacement of the anode with a fresh lithium sheet. The utilization of the electrochemically active sulfur was about 90 % assuming a complete reaction to the product, Li 2 S.