The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O2−, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO2 in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO2 can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O2/CO2 battery is developed. The CO2 not only facilitates the in situ formation of a passivated protective Li2CO3 film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O2−. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li2CO3. The Li–O2/CO2 battery achieves a full discharge capacity of 6628 mAh g−1 and a long life of 715 cycles, which is even better than those of pure Li–O2 batteries. CO2 can do: CO2 makes Li–O2 batteries more stable. On the anode side, CO2 can facilitate the formation of a protective and self‐healing Li2CO3 film, which can expel the H2O and aggressive intermediates during cycling. The cathode and electrolyte are also protected because the O2− intermediate is captured by CO2 to prevent the formation of 1O2.