The Li-S battery is a promising next-generation technology due to high theoretical energy density (2600Wh kg-1) and low materials cost. However, poor cycling stability and coulombic efficiency caused by polysulfide dissolution/shuttling have impeded its practical implementation. In this talk, I will introduce a novel strategy to suppress notorious polysulfide dissolution using hydrofluoroethers (HFEs) with bi-functional, surfactant-like amphiphilic design: a polar lithiophilic “head” attached to a fluorinated lithiophobic “tail.” A unique solvation mechanism is proposed for these solvents whereby dissociated lithium ions are readily coordinated with lithiophilic “head” to induce self-assembly into micelle-like complex structures. Complex formation is verified experimentally by changing the additive structure and concentration using small angle X-ray scattering (SAXS). These HFE-based electrolytes are found to prevent polysulfide dissolution and to have excellent chemical compatibility with lithium metal, evidenced by superior cell performance: Li||Cu stripping/plating tests reveal high coulombic efficiency (>99.5%), modest polarization, and smooth surface morphology of the deposited lithium. Li-S cells are demonstrated with 1395 mAh g-1 initial capacity and 71.9% retention over 100 cycles at >99.5% efficiency.