The pre-edge peak predominantly emanates from the terminal sulfur in each polysulfide, with its intensity influenced by varying amounts of internal sulfur coexisting with the terminal sulfur. Elemental sulfur (S8), lacking a pre-edge peak, solely exhibits the main peak at 2473.3 eV, symbolizing a cyclic structure without terminal groups. Noteworthy is that Li2S8 to Li2S4 also display the same main peak at 2473.3 eV, attributable to the long-chain and middle-chain polysulfides partially containing the cyclic structure pattern of internal sulfur. Conversely, the Li2S sample lacks a pre-edge peak and its main peak shifts from 2473.3 to 2474.2 eV. This shift results from an increased charge from the sole terminal sulfur, inducing a reduced binding energy of the 1s core electrons and conspiring to instigate a "red shift" in the absorption onset of the terminal atoms. The operando XAS spectra were collected at the first discharge cycle at a C-rate of C/10