A　strategy　for　one-dimensional　nanofibrous　Co@N-C　oxygen　reduction　reaction　(ORR)　electrocatalysts　was　developed　using　nanofibrillated　cellulose　(NFC)　as　the　scaffold　material.　In　situ　coupling　of　a　Co-adenine　(Co-Ad)　complex　on　an　NFC　bio-template　leads　to　populated　and　well　spatial　distribution　of　C,　N,　and　Co　active　species　after　pyrolysis,　which　has　a　pivotal　effect　on　facilitating　ORR　via　a　four-electron-dominated　process.　Additionally,　the　internal　abundant　micro-　and　mesopores　in　the　carbon　nanofiber　skeleton　ensure　rapid　mass　transport　and　adequate　exposure　of　active　compositions.　In　combination　with　these　advantages,　the　as-obtained　Co-Ad/NFC-700　demonstrated　superior　ORR　activity　and　endowed　the　fabricated　Zn-air　battery　with　superb　performance:　a　high　peak　power　density　of　167　mW　cm-2,　an　excellent　specific　capacity　of　739　mA　h　g-1,　and　an　excellent　cyclability　exceeding　40　h.　©　2022　American　Chemical　Society.　All　rights　reserved.