The practical applications of lithium–sulfur (Li–S) batteries are seriously limited by the undesirable polysulfide shuttling and lithium dendrite growth. Herein, a multifunctional membrane is designed and prepared by coating a lithiated Nafion (Li@Nafion) layer and an Al2O3 layer on the two sides of a routine polymer membrane (polypropylene/polyethylene/polypropylene, PEP). The Li@Nafion layer faced to the sulfur cathode builds a “polysulfide‐phobic” surface to restrain the shuttle effect via Coulomb repulsion, while the Al2O3 layer with a uniform porous structure aids in regulating homogeneous Li+ fluxes to achieve stable Li electrodeposition. As a result, the Li//Li symmetric cell with a Li@Nafion/PEP/Al2O3 (LNPA) separator realizes stable Li plating/striping even after 1000 h at a high current density (5 mA cm−2). Moreover, the Li–S batteries incorporating LNPA separators not only can achieve excellent outstanding cyclic stability at an ultrahigh sulfur loading (7.6 mg cm−2), but also exhibit impressive electrochemical performance at an elevated temperature (60 °C). The rational design of the LNPA separator presents new insights to develop high‐performance Li–S batteries.