AbstractZn‐CO2 batteries (ZCBs) are promising for CO2 conversion and electric energy release. However, the ZCBs couple the electrochemical CO2 reduction (ECO2R) with the oxygen evolution reaction and competitive hydrogen evolution reaction, which normally causes ultrahigh charge voltage and CO2 conversion efficiency attenuation, thereby resulting in ~90% total power consumption. Herein, isolated FeN3 sites encapsulated in hierarchical porous carbon nanoboxes (Fe‐HPCN, derived from the thermal activation process of ferrocene and polydopamine‐coated cubic ZIF‐8) were proposed for hydrazine‐assisted rechargeable ZCBs based on ECO2R (discharging process: CO2 + 2H+ → CO + H2O) and hydrazine oxidation reaction (HzOR, charging process: N2H4 + 4OH− → N2 + 4H2O + 4e−). The isolated FeN3 endows the HzOR with a lower overpotential and boosts the ECO2R with a 96% CO Faraday efficiency (FECO). Benefitting from the bifunctional ECO2R and HzOR catalytic activities, the homemade hydrazine‐assisted rechargeable ZCBs assembled with the Fe‐HPCN air cathode exhibited an ultralow charge voltage (decreasing by ~1.84 V), excellent CO selectivity (FECO close to 100%), and high 89% energy efficiency. In situ infrared spectroscopy confirmed that Fe‐HPCN can generate rate‐determining *N2 and *CO intermediates during HzOR and ECO2R. This paper proposes FeN3 centers for bifunctional ECO2R/HzOR performance and further presents the pioneering achievements of ECO2R and HzOR for hydrazine‐assisted rechargeable ZCBs.