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Exploring non-noble metal and high-activity electrocatalysts through a simple and controllable protocol remains a great challenge for oxygen reduction reaction (ORR) and zinc-air batteries.Herein,we developed a melt polymerization strategy to synthesize iron-polyphthalocyanine (FePPc) metallic-organic frameworks (MOFs)over the carbon black matrix (FePPc@CB).Through noncovalent π-π interactions,FePPc molecules can anchor on carbon matrix,thus facilitating the electron transfer process and stabilizing the systems.Owing to abundant free electrons and atomically MN4 catalytic sites in the macrocycle structure,FePPc@CB exhibits excellent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalytic activity.The FePPc@CB also delivers excellent performances for liquid and flexible all-solidstate batteries compared to that of commercial Pt/C,making it a promising ORR/OER electrocatalyst.