It has been demonstrated that formation of short sulfur chains connecting DIB molecules are thermodynamically more favorable. It has also been observed experimentally that formation of higher-order Li-polysulfides which can dissolve in the electrolyte is largely hindered during discharge in S/DIB copolymers containing short sulfur chains. Therefore, a stable cycling for 1500 cycles has been reported. This clearly emphasizes the need for a synthesis strategy which facilitates the formation of S/DIB copolymers with short sulfur chains in a controllable way. The present study shows that Raman spectroscopy is a powerful tool to investigate structural properties of S/DIB copolymers and provides a way to probe the