Atomic　metal　catalysis　(AMC)　provides　an　effective　way　to　enhance　activity　for　the　oxygen　reduction　reaction　(ORR).　Cobalt　anchored　on　nitrogen-doped　carbon　materials　have　been　extensively　reported.　The　carbon-hosted　Co-N4　structure　was　widely　considered　as　the　active　site;　however,　it　is　very　rare　to　investigate　the　activity　of　Co　partially　coordinated　with　N,　for　example,　Co-N4−xCx.　Herein,　the　activity　of　Co-N4−xCx　with　tunable　coordination　environment　is　investigated　as　the　active　sites　for　ORR　catalysis.　The　defect　(di-vacancies)　on　carbon　is　essential　for　the　formation　of　Co-N4−xCx.　N　species　play　two　important　roles　in　promoting　the　intrinsic　activity　of　atomic　metal　catalyst:　N　coordinated　with　Co　to　manipulate　the　reactivity　by　modification　of　electronic　distribution　and　N　helped　to　trap　more　Co　to　increase　the　number　of　active　sites.　©　2020　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim