Lithium-sulfur (Li-S) batteries are one of the promising candidates as the next generation energy storage devices, suitable for various mobile and stationary electronics. In this work, hierarchical porous carbon derived through $CO_2$ conversion is used as the host material for a cathode in Li-S batteries. $NaBH_4$ is used as a reducing agent and $CaCO_3$ as a nano-template to synthesize the hierarchical porous carbon named CPC. The S/C composite fabricated through melt diffusion technique contains high sulfur content above 80 wt% due to the large pore volume of CPC, especially in mesoporous area. S/C composite alleviates the shuttle effect and provides a conductive pathway for charge transfer. Moreover, carbon nanofiber (CNF) interlayer is used in combination to achieve a high initial capacity of 1105 mAh/g and discharge capacity of 687 mAh/g after 100 cycles at 0.2 C. The novelty of this work lies on introducing $CO_2$ derived CPC to synthesize S/C composite in combination with the CNF interlayer to enhance the performance of Li-S batteries.