Durable and highly efficient electrocatalysts for the oxygen reduction reaction (ORR) are central to rechargeable Zn–air batteries (ZABs). The current best-performing ORR electrocatalysts are FeN₄-based powder materials among the non-noble metals, but they still suffer from peeling off and demetallation during long-term device operation. Herein, we constructed an anti-dissolving structure of dual-atomic Fe sites modified with carbon holes and pyridinic-N on carbon fiber membranes (Fe₂N₆-CMPCFs) as binder-free cathodes via two-step NH₃-assisted carbonization. Experimental and theoretical studies implied that the energy barrier of Fe dissolution is significantly higher in Fe₂N₆-CMPCFs (1.41 eV) compared to that of conventional non-defective FeN₄ (0.94 eV), which can significantly inhibit the demetallation of Fe sites during long-term electrocatalysis. Thus, the Fe₂N₆-CMPCFs-based cathode enabled ZABs to operate over 200 days (record-breaking 14 500 cycles) with a remarkable peak power density of 261.4 mW cm⁻². Furthermore, structure analysis uncovered the anti-dissolving origin of Fe sites in Fe₂N₆-CMPCFs, which can be attributed to the enhanced orbital interaction (Fe–N and Fe–Fe) and electrostatic force between the Fe and N atoms. This work provides a valuable route to design anti-dissolving atomic sites and binder-free cathodes for sustainable electronic devices.