Rechargeable Li−O2 batteries represent a highly attractive battery technology, owing to a high theoretical energy density of 3500 Wh kg−1, but they suffer from large charging polarization and lithium anode degradation on cycling. Herein, we report a Li−O2 battery system with reduced polarization and a long lifespan, which is realized by using a novel [email protected] P composite anode integrated with lithium iodide in ether-based electrolyte. Coating a Super P carbon layer, with an optimal thickness of approximately 30 μm, onto the lithium anode results in a lowered interface impedance and a decreased Li depositing/stripping overpotential (<15 mV) over 300 cycles at 0.3 mA cm−2. The Li−O2 batteries assembled with the [email protected] P anode and LiI additive could mitigate the detrimental shuttling effect of I3− and deliver a high reversible capacity of 1000 mAh g−1 with a median charge voltage lower than 3.3 V after 50 cycles. This study provides a simple yet effective way to protect the lithium anode and design high-performance Li−O2 batteries.