The　rational　control　of　the　active　site　of　metal-organic　frameworks　(MOFs)　derived　nanomaterials　is　essential　to　build　efficient　bifunctional　oxygen　reduction/evolution　reaction　(ORR/OER)　catalysts.　Accordingly,　through　designing　and　constructing　a　Co3O4-Co　heterostructure　embedded　in　Co,　N　co-doped　carbon　polyhedra　derived　(Co3O4-Co@NC)　from　the　in-situ　compositions　of　ZIF-67　and　cobalt　nanocrystals　synthesized　by　the　strategy　of　in-situ　NaBH4　reduction,　the　dual-active　site　(Co3O4-Co　and　Co-Nx)　is　synchronously　realized　in　a　MOFs　derived　nanomaterials.　The　formed　Co3O4-Co@NC　shows　excellent　bifunctional　electrocatalytic　activity　with　ultra-small　potential　gap　(ΔE　=　Ej=10　(OER)　−　E1/2　(ORR))　of　0.72　V,　which　surpasses　the　commercial　Pt/C　and　RuO2　catalysts.　The　theory　calculation　results　reveal　that　the　excellent　bifunctional　electrocatalytic　activity　can　be　attributed　to　the　charge　redistribution　of　Co　of　Co-Nx　induced　by　the　synergistic　effects　of　well-tuned　active　sites　of　Co3O4-Co　nanoparticle　and　Co-Nx,　thus　optimizing　the　rate-determining　step　of　the　desorption　of　O2*　intermediate　in　ORR　and　OH*　intermediate　in　OER.　The　rechargeable　Zn-air　batteries　with　our　bifunctional　catalysts　exhibit　superior　performance　as　well　as　high　cycling　stability.　This　simple-effective　optimization　strategy　offers　prospects　for　tuning　the　active　site　of　MOF　derived　bifunctional　catalyst　in　electrochemical　energy　devices.　[Figure　not　available:　see　fulltext.]　©　2020,　Tsinghua　University　Press　and　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature.