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Magnesium/sulfur battery (Mg/S) has recently received wide attention due to its high theoretical energy density (3,260 Wh/L) and low cost. To further improve its safety and flexibility, developing a polymer electrolyte that can be compatible with both electrophilic S and Mg is critical. Here, we report a magnesium chloride-(fluorinated tetraethylene glycolic)borate (MgCl-FTGB) based non-nucleophilic, gel-type polymer electrolyte for Mg/S battery via a facile synthetic method through commercially available reagents. This electrolyte coupled with glass fiber allows reversible Mg deposition/dissolution (100% coulombic efficiency) with low polarization (500 μA/cm2, 300/300 mV), and shows a wide electrochemical window of 4.8 V (vs. Mg/Mg2+). Mg/S battery assembled with this electrolyte can cycle over 50 times with a high specific discharge capacity retention of over 1,100 mAh/g.