Lithium-sulfur (Li-S) batteries have emerged as a focal point of research and development in recent years, driven by their compelling advantages as potential harbingers of energy storage technology beyond the current state-of-the-art Li-ion batteries (LIBs). With a remarkable combination of high theoretical energy density, cost-effectiveness, and the widespread availability of sulfur, Li-S batteries stand out as a promising contender for the next generation of energy storage solutions. The theoretical energy density of Li-S batteries have a fivefold increase compared to that of conventional LIBs, positioning them as an optimal choice for both electric vehicles and grid-scale energy storage applications. The exceptional energy density of Li-S batteries is predominantly attributed to sulfur serving as the cathode active material, boasting a theoretical capacity of 1675 mAh/gsulfur, significantly surpassing traditional cathode materials like cobalt, nickel, and manganese oxides used in LIBs. Furthermore, sulfur's non-toxic nature and abundant supply make it an attractive and sustainable choice for energy storage applications. In essence, the remarkable energy density inherent in Li-S batteries confers practical viability to their integration into energy storage systems. Meanwhile, their abundant natural availability concurrently establishes a resilient basis for the expansive commercialization prospects of Li-S batteries on a large scale. Despite the substantial merits offered by Li-S batteries in terms of their elevated theoretical energy density and cost-effectiveness, the realization of their commercial potential necessitates the resolution of formidable technical challenges. These challenges encompass the low conductivity of elemental sulfur, parasitic reactions on the anode, and the volume expansions during lithiation and de-lithiation processes. Within this spectrum, two primary concerns have been scrutinized extensively within the domains of chemistry and electrochemistry. Firstly, materials and porous separators, including carbon nanotubes and MXenes, polymer and ceramic membranes, offer an additional avenue by effectively entrapping polysulfides and impeding their diffusion towards the anode. Furthermore, the deployment of solid-state electrolytes emerges as a promising strategy, circumventing the polysulfide shuttling effect by eliminating the reliance on liquid electrolytes, which are susceptible to intermediate polysulfide dissolution. Despite extensive efforts to pave the way for the commercialization of Li-S batteries, existing research primarily concentrates on modifying the cathode host structure by incorporating various active sites for polysulfide catalysis and employing hollow, porous matrices to trap polysulfides and prevent their migration. However, to our best knowledge, a bifunctional electrolyte additive simultaneously focusing on enhancing polysulfides conversion and anchoring soluble polysulfide has not been well defined, and a comprehensive study of the underlying mechanism of such bifunctional additive needs to be addressed.