Covalent Dangling of Poly‐Indium‐Phthalocyanine Over Carbon Nanopits as Superior Oxygen Reduction Catalyst for Flexible Zn‐Air Battery

Abstract Oxygen reduction reaction (ORR) represents a cornerstone in renewable energy technologies such as Zn–air batteries, yet its sluggish kinetics and reliance on noble metal catalysts remain critical bottlenecks. Here, we report an ingenious catalyst configured by covalently dangling poly‐indium‐phthalocyanine onto carbon nanopit defects in carbon nanotubes (InPPc/v‐CNTs). This architecture induces axial In–C coordination that disrupts the symmetric electron distribution of the planar In–N 4 center and strengthens electronic metal–support interactions. Theoretical calculations reveal that this distorted electronic environment enhances O 2 adsorption/dissociation kinetics while weakening the *OH desorption energy barrier, thereby synergistically boosting ORR kinetics. Benefiting from the tailored electronic structure and optimized metal–support configuration, InPPc/v‐CNTs exhibits both superb ORR activity and stability, with a half‐wave potential up to 0.90 V vs RHE and a kinetic current density of 42.9 mA cm −2 (>10‐fold higher than the Pt/C benchmark). Moreover, in aqueous Zn–air batteries, it delivers a remarkable power density of 270 mW cm −2 and a discharge stability up to 865 h at 5 mA cm −2 . This work transcends conventional catalyst design by unifying defect engineering, electronic asymmetry, and macromolecular stabilization into a cohesive framework, establishing a new paradigm for metal phthalocyanine‐based ORR catalysts.