The preparation of a sulfur/dehydrogenated polyacrylonitrile (S/DPAN) composite by manual mixing followed by heat treatment at 300 °C in argon atmosphere is described. Electron microscopy analysis reveals very different morphology before and after heat treatment of the composites. Manually mixed S/DPAN cathode composites containing 48 wt% of sulfur exhibit a stable discharge capacity of 1050 mAh g−1 after 80 galvanostatic discharge–charge cycles at 0.2C, and good C-rate performance with up to 770 mAh g−1 at 1C. Results indicate that the long chains of polyacrylonitrile are retained during synthesis and may contribute to the enhanced electronic conductivity of the composite.