Reasonably screening the targeted oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) constituents and constructing high-efficiency and stabilized ORR/OER bifunctional electrocatalysts are pivotal for the advancement of rechargeable zinc-air batteries (ZABs). Here, CoFe layered double hydroxide (CoFe-LDH) nanosheets are deposited on nitrogen-doped graphite-carbon polyhedra with FeCo alloy nanoparticles (FeCo/LDH-NGCP). Due to the synergic effect between FeCo-NGCP, CoFe-LDH and FeCo/LDH-NGCP, the electrocatalyst with the abundant and accessible active sites can provide good charge/mass transfer, and thus shows wonderful ORR and OER bifunctional electrocatalytic performance. In ORR tests, FeCo/LDH-NGCP catalyst displays larger half-wave potential (E