Nevertheless, to this day neither the lithiation mechanism of S/DIB copolymer cathodes has been entirely resolved at an atomistic level, nor their structural evolution during the discharge has been fully understood. A first step towards understanding the discharge mechanism of the S/DIB copolymers is to decipher their structural properties at the fully charged state of the battery, where no lithiation reaction has occurred. It has been recently found that short S n chains (n ≃4) show a higher formation probability compared to other sulfur chain lengths. It has also been observed that the stability of S/DIB copolymers is brought about by the formation of short S chains. In addition, short S chains have been predicted and reported to be more favorable in other sulfur/carbon copolymer materials involving organic groups interconnected via sulfur chains. The formation of Li-polysulfides during discharge has been shown to be largely hindered in S/DIB copolymer cathode involving short S chains and therefore, they exhibit a much better performance in terms of cycle life. Therefore, a strategy for the synthesis of S/DIB copolymers as well as their structural modification is highly called for, in which the formation of S n chains with short lengths (n ≤ 4) has the highest probability.