The　construction　and　design　of　highly　efficient　and　inexpensive　bifunctional　oxygen　electrocatalysts　substitute　for　noble-metal-based　catalysts　is　highly　desirable　for　the　development　of　rechargeable　Zn-air　battery　(ZAB).　In　this　work,　a　bifunctional　oxygen　electrocatalysts　of　based　on　ultrafine　CoFe　alloy　(4-5　nm)　dispersed　in　defects　enriched　hollow　porous　Co-N-doped　carbons,　made　by　annealing　SiO2　coated　zeolitic　imidazolate　framework-67　(ZIF-67)　encapsulated　Fe　ions.　The　hollow　porous　structure　not　only　exposed　the　active　sites　inside　ZIF-67,　but　also　provided　efficient　charge　and　mass　transfer.　The　strong　synergetic　coupling　among　high-density　CoFe　alloys　and　Co-Nx　sites　in　Co,　N-doped　carbon　species　ensures　high　oxygen　reduction　reaction　(ORR)　and　oxygen　evolution　reaction　(OER)　activity.　First-principles　simulations　reveal　that　the　synergistic　promotion　effect　between　CoFe　alloy　and　Co-N　site　effectively　reduced　the　formation　energy　of　from　O*　to　OH*.　The　optimized　CoFe-Co@PNC　exhibits　outstanding　electrocatalytic　stability　and　activity　with　the　overpotential　of　only　320　mV　for　OER　at　10　mA·cm−2　and　the　half-wave　potential　of　0.887　V　for　ORR,　outperforming　that　of　most　recent　reported　bifunctional　electrocatalysts.　A　rechargeable　ZAB　constructed　with　CoFe-Co@PNC　as　the　air　cathode　displays　long-term　cyclability　for　over　200　h　and　high　power　density　(152.8　mW·cm−2).　Flexible　solid-state　ZAB　with　our　CoFe-Co@PNC　as　the　air　cathode　possesses　a　high　open　circuit　potential　(OCP)　up　to　1.46　V　as　well　as　good　bending　flexibility.　This　universal　structure　design　provides　an　attractive　and　instructive　model　for　the　application　of　nanomaterials　derived　from　MOF　in　the　field　of　sustainable　flexible　energy　applications　device.　[Figure　not　available:　see　fulltext.]　©　2020,　Tsinghua　University　Press　and　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature.