Abstract Rechargeable Zn–air batteries (ZABs) are promising for energy storage and conversion. However, the high charging voltage and low energy efficiency hinder their commercialization. Herein, these challenges are addressed by employing precisely constructed multifunctional Fe–Co diatomic site catalysts (FeCo‐DACs) and integrating iodide/iodate redox into ZABs to create Zinc–air/iodide hybrid batteries (ZAIHBs) with highly efficient multifunctional catalyst. The strong coupling between the 3d orbitals of Fe and Co weakens the excessively strong binding strength between active sites and intermediates, enhancing the catalytic activities for oxygen reduction/evolution reaction and iodide/iodate redox. Consequently, FeCo‐DACs exhibit outstanding bifunctional oxygen catalytic activity with a small potential gap (Δ E = 0.66 V) and outstanding stability. Moreover, an outstanding catalytic performance toward iodide/iodate redox is obtained. Therefore, FeCo‐DAC‐based ZAIHBs exhibit high energy efficiency of up to 75% at 10 mA cm −2 and excellent cycling stability (72% after 500 h). This research offers critical insights into the rational design of DACs and paves the way for high‐energy efficiency energy storage devices.
