Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze‐casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P‐doped carbon aerogel incorporating in situ grown FeP/Fe2O3 nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g−1 at a current density of 20 mA cm−2 with a good long‐term durability, outperforming those assembled with commercial Pt/C+RuO2 catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid‐state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g−1 and an energy density of 517 Wh kg−1 at 5 mA cm−2 together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.