Heterojunctions are a promising class of materials for high‐efficiency bifunctional oxygen electrocatalysts in both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, the conventional theories fail to explain why many catalysts behave differently in ORR and OER, despite a reversible path (^*O₂⇋^*OOH⇋^*O⇋^*OH). This study proposes the electron‐/hole‐rich catalytic center theory (e/h‐CCT) to supplement the existing theories, it suggests that the Fermi level of catalysts determines the direction of electron transfer, which affects the direction of the oxidation/reduction reaction, and the density of states (DOS) near the Fermi level determines the accessibility for injecting electrons and holes. Additionally, heterojunctions with different Fermi levels form electron‐/hole‐rich catalytic centers near the Fermi levels to promote ORR/OER, respectively. To verify the universality of the e/h‐CCT theory, this study reveals the randomly synthesized heterostructural Fe₃N‐FeN_0.0324 (Fe _x N@PC with DFT calculations and electrochemical tests. The results show that the heterostructural F₃N‐FeN_0.0324 facilitates the catalytic activities for ORR and OER simultaneously by forming an internal electron‐/hole‐rich interface. The rechargeable ZABs with Fe _x N@PC cathode display a high open circuit potential of 1.504 V, high power density of 223.67 mW cm⁻², high specific capacity of 766.20 mAh g⁻¹ at 5 mA cm⁻², and excellent stability for over 300 h.