In　carbon-based　oxygen　reduction　reaction　(ORR)　catalysts,　metal-free　nitrogen-doped　carbon-based　materials　generally　have　higher　catalytic　stability　compared　to　metal　catalysts　with　reduced　catalytic　activity　due　to　the　occurrence　of　metal　agglomeration　during　the　catalytic　reaction.　In　this　paper,　a　metal-free　nitrogen-doped　carbon-based　ORR　catalyst　NCOH5-900　with　a　half-wave　potential　of　0.846　V　and　onset　potential　of　0.94　V　was　prepared　using　coal　as　the　carbon　source,　dicyandiamide　as　the　nitrogen　source　and　KOH　as　the　activator.　The　material　has　good　ORR　catalytic　performance　with　half-wave　potential　and　onset　potential　comparable　to　Pt/C　catalyst　with　the　same　mass　loading,　with　better　resistance　to　methanol　toxicity　and　catalytic　stability.　The　physical　and　chemical　properties　of　the　prepared　catalyst　were　controlled　by　adjusting　the　amount　of　nitrogen　doping　and　activation　temperature　to　establish　the　relationship　between　the　material　structure　and　the　ORR　performance.　The　results　suggest　that　for　the　metal-free　nitrogen-doped　carbon-based　material,　the　good　ORR　catalytic　performance　is　attributed　to　the　abundant　edge　defects,　high　graphitization,　good　mixed　structure　of　micro/mesopores,　large　nitrogen　content,　and　high　ratio　of　pyridine　to　graphitic　nitrogen.　Finally,　the　catalytic　mechanism　of　NCOH5-900　for　ORR　is　investigated　using　in-situ　attenuated　total　reflection　Fourier　infrared　(ATR-FTIR)　and　in-situ　Raman,　confirming　the　four-electron　reduction　process　of　O2　via　a　continuous　dual　step　of　two-electron　transfer　process.　©　2024