In this study, we aim to address the structural evolution of S/DIB copolymers during discharge by performing finite-temperature Raman spectroscopy simulations, combining quantum-chemical calculations with ab initio molecular dynamics simulations on model S/DIB systems. Here, we study the lithiation reactions of DIB-S n -DIB with two different sulfur chain lengths, namely n = 4 and 8, and focus on Raman spectroscopic fingerprints of the final structures at different stages of discharge. The huge computational effort of such an investigation is substantially reduced by our efficient Wannier polarizability method for the estimation of the dynamics of polarizability tensors during ab initio molecular dynamics simulations, fully bypassing the time-consuming linear response calculations.