Zinc–air batteries (ZABs) and anion exchange membrane water electrolyzers (AEMWEs) are promising technologies for grid-scale energy storage and sustainable hydrogen production, but their efficiency is limited by sluggish oxygen reduction (ORR) and oxygen evolution (OER) kinetics and catalyst instability. Herein, we report a robust cobalt–nitrogen–carbon (Co–N–C) catalyst derived from a metal–organic framework, featuring metallic Co and Co–N4 active sites in Co–N–C catalysts and structurally different Co3O4 nanostructures. Optimizing the local coordination environment promotes charge transfer at the Co centers and strengthens interactions with the N-doped carbon matrix, enabling superior bifunctional activity. The catalyst delivers a half-wave potential of 0.857 V for the ORR and a low overpotential of 1.55 V RHE at 10 mA cm−2 for the OER, with remarkable stability for 10 000 cycles. Device-level evaluation demonstrates a peak power density of 257 mW cm−2 in ZABs and a sustained current density of 465 mA cm−2 at 1.8 V in AEMWEs, surpassing the performance of most reported Co–N–C catalysts. In situ Raman and X-ray absorption spectroscopy (metallic cobalt as the primary active site in Co–N–C), supported by density functional theory, identify Co–N4 moieties as the secondary active sites, as compared to trans-CoCN2 and cis-CoCN2 in Co–N–C. This work provides structure–activity insights for Co–N–C catalysts, advancing the design of next-generation bifunctional electrocatalysts for sustainable energy conversion.