Multi-dimensional　hierarchical　nanostructures　can　efficiently　promote　the　mass　transportation　and　electron　transfer　of　electrocatalysts,　which　can　boost　the　electrocatalytic　performance.　In　this　study,　we　report　the　design　of　a　hierarchical　carbon/metal　nanostructure　(Co@CNFs)　with　the　combination　of　0D　cobalt　metal　nanoparticles,　1D　carbon　nanofibers,　and　2D　carbon　nanosheets　as　a　bifunctional　oxygen　reduction/evolution　reaction　(ORR/OER)　catalyst.　The　Co@CNF　catalysts　are　prepared　by　using　a　facile　approach　of　combining　electrospinning,　impregnation　growth　of　ZIF-67　nanosheets,　and　high-temperature　carbonization.　Through　rationally　optimizing　the　synthesis　conditions,　including　the　chemical　concentration　and　carbonization　temperature,　the　optimal　catalyst　of　Co@CNFs-50-800　features　a　hierarchical　structure　of　continuous　carbon　nanofibers　(CNFs)-anchored　carbon　nanosheets　wrapping　Co　nanoparticles,　which　holds　decent　catalytic　activities　in　term　of　a　half-wave　potential　of　0.8　V　for　the　ORR　and　a　potential　of　1.54　V　for　the　OER　at　10　mA　cm−2.　A　rechargeable　Zn-air　battery　is　set　up　using　the　catalyst　as　the　air　cathode,　which　exhibits　a　high　specific　capacity　of　809　mAh　g−1　and　a　peak　power　density　of　165.5　mW　cm−2,　as　well　as　a　good　durability　up　to　1000　charging-discharging　cycles　(＞160　h),　which　is　even　better　than　the　benchmark　Pt/C+RuO2　catalyst.　This　study　provides　a　rational　strategy　to　design　hierarchically　nanostructural　catalysts　to　boost　the　mass　transportation　and　electron　transfer　of　electrocatalytic　reactions.　©　2021　Wiley-VCH　GmbH