This study reports on a novel approach to fabrication of carbon-sulfur composite material and demonstrates its application as cathode for Li–S batteries. Firstly, highly porous carbon material has been prepared by exploiting PMMA colloidal crystal arrays as sacrificial template and subsequently mixing with elemental sulfur at 155 °C. The resulting carbon-sulfur composite cathode material possess very high intrinsic surface area, conductivity and has been found to demonstrate as high as 1600 mAh g− 1 capacity in 1st discharge cycle and about 300–400 mAh g− 1 in 50th discharge cycle.