Developing bifunctional catalysts for the ORR and OER, along with a unique cathode structure, is essential for advancing rechargeable zinc-air batteries (ZABs) and aluminum-air batteries (AABs). Our catalyst (NiFe LDH A-FeSACoSA-FeCoAlloy-CNT/NC) integrates nickel-iron layered double hydroxide (NiFe LDH), iron-cobalt dual single atoms (FeSACoSA), and iron-cobalt nanoalloy (FeCoAlloy) within carbon nanotubes (CNTs) on a nitrogen-doped carbon framework (NC). Due to its distinctive features, this catalyst excels, achieving an ORR half-wave potential of 0.84 V and an OER potential of 1.56 V (Ej=10mAcm−2). In ZABs, it outperforms the Pt/C+RuO2, reaching a power density of 266 mWcm−2 and demonstrating impressive rechargeability over 495 h (1484 cycles). Flexible ZABs achieve 173 mWcm−2 and over 270 cycles (90 h), while flexible AABs reach 145 mWcm−2, surpassing Pt/C+RuO2. Exceptional performance in terms of capacity, power density, rechargeability, and lifespan is attributed to the catalyst's design and the cathode configuration's unique attributes. Display omitted •The catalyst was synthesized via Schiff reaction, carbonization and NH3 processes.•The catalyst shows an excellent bifunctional characteristics of ORR and OER.•The ZAB demonstrates 809 mAh g−1 at 50 mA cm−2 and 266 mW cm−2 at 381 mA cm−2.•The flexible ZAB shows 710.8 mAh g−1 at 1 mA cm−2 and 173 mW cm−2 at 182 mA cm−2.•The flexible AABs reach 120.7 mAh g−1 at 1 mA cm−2 and 145 mW cm−2 at 157 mA cm−2.