In this study, we introduce bis(4-nitrophenyl) carbonate (BNC) as an electrolyte additive aimed to parallelly modify the Li + solvation structure with intermediate polysulfides (Li2Sx, 1<x<8) for enhanced SRR kinetics as a solvation-property modifier, and to anchor the soluble polysulfides from migration as a polysulfide mediator. BNC was initially reported by Yang and Goodenough et al. in a Li-S battery study. However, the previous research lacked an in-depth probe of the solvation modification induced by BNC and optimization of BNC concentrations for optimal performance, leaving room for more precise characterization methods of the BNCinfluenced SRR pathway. This study employed density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to predict solvation modification in the presence of BNC. Validation of computational modeling predictions is accomplished by nuclear magnetic resonance (NMR), revealing a more de-shielded coordination environment for lithium. In situ electrochemical impedance spectroscopy (EIS) and activation energy comparisons across different electrolyte systems further confirm the specific improved kinetics of lithium polysulfides conversion at various depths of discharge (DoD). Operando Raman and operando X-ray absorption spectroscopy (XAS) provide crucial insights into lithium polysulfides formation, offering additional evidence of the dual impact of BNC on the kinetics of the SRR and suppression of the polysulfide shuttling effect. X-ray fluorescence (XRF) mapping coupled with X-ray absorption near edge spectroscopy (XANES) elucidates the detailed mechanism of suppressing the polysulfide shuttling effect. The enhanced lithium-ion transportation accelerates lithium polysulfides conversion kinetics, and superior anchoring efficiency of soluble polysulfides result in a notable 87.58% capacity retention of 678.8 mAh/gsulfur at C-rate of C/5 (0.12% capacity decay per cycle) with a columbic efficiency of 97.4% over prolonged cycles at a sulfur loading of 4 mg/cm 2 . These metrics stand favorably against current state-of-the-art examples in Li-S batteries and shed light on the advanced design of electrolyte.