Operando Raman is a practical technique for monitoring chemical reaction pathways without any destructive interruptions, as demonstrated in our previous research. The Raman spectroscopy cell is illustrated in Figures and. Figures and present conventional Raman spectra of a Li-S battery using the baseline electrolyte. Throughout a typical discharge process, elemental sulfur (S8) undergoes a conversion sequence, transforming into long-chain polysulfides (Li2Sx, 6<x<8), followed by middle-chain polysulfides (Li2Sx, 3<x<5), and ultimately into short-chain polysulfides, also referred to as insoluble polysulfides (Li2Sx, 1<x<2). In Figure , the characteristic Raman shift peak of elemental sulfur is identified at 217 cm -1 in black. The two major intermediates, long-chain and middle-chain polysulfides, are denoted by red and blue colors, showcasing their characteristic Raman shifts at 400 and 453 cm -1 , respectively. These peak assignments align with our ex-situ samples (Figure ) and previous studies.