Nitrogen-coordinated single-atom catalysts (SACs) have emerged as a frontier for electrocatalysis (such as oxygen reduction) with maximized atom utilization and highly catalytic activity. The precise design and operable synthesis of SACs are vital for practical applications but remain challenging because the commonly used high-temperature treatments always result in unpredictable structural changes and randomly created single atoms. Here, we develop a pyrolysis-free synthetic approach to prepare SACs with a high electrocatalytic activity using a fully π-conjugated iron phthalocyanine (FePc)-rich covalent organic framework (COF). Instead of randomly creating Fe-nitrogen moieties on a carbon matrix (Fe-N-C) through pyrolysis, we rivet the atomically well-designed Fe-N-C centers via intermolecular interactions between the COF network and the graphene matrix. The as-synthesized catalysts demonstrate exceptional kinetic current density in oxygen reduction catalysis (four times higher than the benchmark Pt/C) and superior power density and cycling stability in Zn-air batteries compared with Pt/C as air electrodes.