Here, we have demonstrated the successful exfoliation of graphite into a layered material with scotch tape-like exfoliation. Sulfur acts as an exfoliating agent and exfoliates the loosely bounded graphite stacks. The shear force by ball milling provides the force required to overcome the van der Waals force between the layers. The MnO2 nanorods were synthesized using a KMnO4 precursor in a hydrothermal arrangement, and due to their intrinsic chemisorption capability, they were doped for polysulfide trapping. With an initial capacity of 1150 mAh/g achieved by the MnO2 nanorod-doped exfoliate-graphite/sulfur composite material, the material has displayed its application in lithium–sulfur batteries, but its use is not limited; it can be a low-cost eco-friendly solution to various energy storage systems with extensive structural qualities.