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The electrochemical characteristics of sulfurized polyacrylonitrile composite (PAN/S) cathodes were compared with the commonly used carbon/S based composite material. The difference in the working mechanism of these composites was examined.  Analytical investigations were done on both kinds of cathode electrode composites by using two reliable analytical techniques, in-situ UV-Visible spectroscopy and 4-electrode Swagelok cell. This study differentiates the working mechanisms of PAN/S composites from conventional elemental sulphur/carbon composite and also sheds light on factors that could be responsible for capacity fading in case of PAN/S composites.