Redox mediators (RMs) are reported to effectually encourage the inactive decomposition of discharge products in lithium–oxygen batteries (LOBs); however, oxidized RMs and other injurious species still attack the Li anodes. An ionic liquid (IL)‐modified PVDF single‐lithium‐ion conducting composite membrane that can permit Li+ only but blocks anions and other molecules is prepared. The PVDF is combined with the strong‐acid cation styrene exchange resin with cation exchange characteristics to make a heterogeneous composite single‐ionic conductor membrane and the IL modification causes the formation of a more‐dense groove inside the PVDF membrane apparently strengthening the conductivity of the membrane without losing its impermeability to cations and discharge intermediates. The utility of the modified composite PVDF (MCP) separator greatly extends the cycle life of the LOB from 66 to 347 cycles at 1000 mAg−1 and 1000 mAhg−1 compared to cells using glass fiber separators. Rate performance is significantly enhanced at 3000 and 5000 mAg−1, increasing from 33 and 21 cycles to 171 and 137 cycles. The full discharge capacity also expands from 3702 to 51 205 mAhg−1. The MCP separator enables iodide‐assisted cathode processes and improves lithium anode stripping/plating, which is essential to improve the performance of nonelectrolytic LOBs.