Nitrogen-doped graphitic carbon materials hosting single-atom iron (Fe-N-C) are major non-precious metal catalysts for the oxygen reduction reaction (ORR). The nitrogen-coordinated Fe sites are described as the first coordination sphere. As opposed to the good performance in ORR, that in the oxygen evolution reaction (OER) is extremely poor due to the sluggish O-O coupling process, thus hampering the practical applications of rechargeable zinc (Zn)-air batteries. Herein, we succeed in boosting the OER activity of Fe-N-C by additionally incorporating phosphorus atoms into the second coordination sphere, here denoted as P/Fe-N-C. The resulting material exhibits excellent OER activity in 0.1 M KOH with an overpotential as low as 304 mV at a current density of 10 mA cm-2. Even more importantly, they exhibit a remarkably small ORR/OER potential gap of 0.63 V. Theoretical calculations using first-principles density functional theory suggest that the phosphorus enhances the electrocatalytic activity by balancing the*OOH/*O adsorption at the FeN4 sites. When used as an air cathode in a rechargeable Zn-air battery, P/Fe-N-C delivers a charge-discharge performance with a high peak power density of 269 mW cm-2, highlighting its role as the state-of-the-art bifunctional oxygen electrocatalyst.