Among others, sulfur-n-1,3-diisopropenylbenzene (S/DIB) copolymer has shown a promising performance as an active cathode material for Li-S batteries. Structural characterization of S/DIB copolymers has been the subject of several studies so far. For example, similar to other S/C copolymers involving sulfur chains, thermodynamically preferred S/DIB structures consist of short S n chains, n ≃4. The shorter sulfur chains are expected to result in a hindrance in the formation of higher-order Li-polysulfides and consequently a stable cycling of 1500 cycles has been reported. Despite qualitative descriptions of the discharge mechanism of S/DIB copolymer cathodes, an atomistic view on their structural evolution during the lithiation reactions is still lacking.