In Lithium sulfur (Li−S) batteries the sulfur host material is a significant area of research that could impart enhanced conductivity and alleviate the shuttling of polysulfides. In the present study, graphene oxide‐ sulfur, GO‐S was synthesized in melt diffusion method by exploring the two different strategies: Ambient (G2‐M) and Inert (G2‐T) conditions. Within the cathode, efficient storage of S with sufficient space in GO interlayers was outperformed by G2‐T method. Further with PEDOT nanostructures enveloped by oxidative polymerisation proves to be a robust conductive layer and an adsorbing agent. It is evidenced physicochemically by XRD, FTIR, TGA, HR‐SEM. Moreover, in addition to the supporting studies, high binding energies of 168.3 and 169.5 eV confirms the superior performance of PEDOT/GO‐S (G3‐T) as most suitable cathode within the system. The electrochemical behaviour of G3‐T possess very low cell impedance with an excellent cyclic reversibility in CV during (de)lithiation process. At 0.1 C, an initial discharge capacity of 868 mAh g−1 has been achieved confirming a high catalytic activity with a low polarisation potential of (ΔE=0.25) inducing fast reaction kinetics. Thus potential locking of sulfur under inert condition is explored with a proven OCV of 2.3 V with red LED glow.