Our current study dives deeper into understanding the complex discharge mechanisms of S/DIB copolymer cathodes. We have observed that S/DIB copolymers containing short and those consisting of long sulfur chains show similar Raman features at 100% depth of discharge. However, we have found frequency ranges in which short-and long-sulfur chain containing copolymers have distinctive Raman activities during the discharge. For example, the Raman activity at ∼450 cm -1 (S-S stretching) can serve as a fingerprint for distinguishing between local copolymer structures consisting of short and long sulfur chains. Although the corresponding band shows an insignificant intensity at early to mid stages of discharge in S/DIB polymers with short sulfur chains, it shows an intensive band in those containing long sulfur chains from 0% up to 86% depth of discharge. At 100% depth of discharge, where no S-S covalent bond is present, the intensity of this band can become negligibly small in all S/DIB samples. In addition to this, the Raman activities at ∼200 cm -1 during the discharge can also be used to distinguish between short and long sulfur chains. The band at ∼200 cm -1 only appears at fully discharged S/DIB copolymers with short sulfur chains.