Developing efficient, inexpensive, and durable electrocatalysts for the oxygen reduction reaction (ORR) is important for the large‐scale commercialization of fuel cells and metal–air batteries. Herein, a hierarchically porous bimetallic Fe/Co single‐atom‐coordinated N‐doped carbon (Fe/Co‐Nx‐C) electrocatalyst for ORR is synthesized from Fe/Co‐coordinated polyporphyrin using silica template‐assisted and silica‐protection synthetic strategies. In the synthesis, first silica nanoparticles‐embedded, silica‐protected Fe/Co‐polyporphyrin is prepared. It is then pyrolyzed and treated with acidic solution. The resulting Fe/Co‐Nx‐C material has a large specific surface area, large electrochemically active surface area, good conductivity, and catalytically active Fe/Co‐Nx sites. The material exhibits a very good electrocatalytic activity for the ORR in alkaline media, with a half‐wave potential of 0.86 V versus reversible hydrogen electrode, which is better than that of Pt/C (20 wt%). Furthermore, it shows an outstanding operational stability and durability during the reaction. A zinc–air battery (ZAB) assembled using Fe/Co‐Nx‐C as an air‐cathode electrocatalyst gives a high peak power density (152.0 mW cm−2) and shows a good recovery property. Furthermore, the performance of the battery is better than a corresponding ZAB containing Pt/C as an electrocatalyst. The work also demonstrates a synthetic route to a highly active, stable, and scalable single‐atom electrocatalyst for ORR in ZABs.