Nitrogen　(N)-doped　nanocarbons　(NDN)　as　metal-free　catalysts　have　elicited　considerable　attention　toward　selective　oxidation　of　alcohols　with　easily　oxidizable　groups　to　aldehydes　in　the　past　few　years.　However,　finding　a　new　NDN　catalytic　material　that　can　meet　the　requirement　of　the　feasibility　on　the　aerobic　catalytics　for　other　complicated　alcohols　is　a　big　challenge.　The　real　active　sites　and　the　corresponding　mechanisms　on　NDN　are　still　unambiguous　because　of　inevitable　coexistence　of　diverse　edge　sites　and　N　species　based　on　recently　reported　doping　methods.　Here,　four　NDN　catalysts　with　enriched　pyridinic　N　species　and　without　any　graphitic　N　species　are　simply　fabricated　via　a　chemical-vapor-deposition-like　method.　The　results　of　X-ray　photoelectron　spectroscopy　and　X-ray　absorption　near-edge　structure　spectra　suggest　that　the　dominating　N　species　on　NDN　are　pyridinic　N.　It　is　demonstrated　that　NDN　catalysts　perform　impressive　reactivity　for　aerobic　oxidation　of　complicated　alcohols　at　an　atmospheric　pressure.　Eleven　kinds　of　aromatic　molecules　with　single　N　species　and　tunable　πconjugation　systems　are　used　as　model　catalysts　to　experimentally　identify　the　actual　role　of　each　N　species　at　a　real　molecular　level.　It　is　suggested　that　pyridinic　N　species　play　an　unexpected　role　in　catalytic　reactions.　Neighboring　carbon　atoms　in　pyridinic　N　species　are　responsible　for　facilitating　the　rate-determining　step　process　clarified　by　kinetic　isotope　effects,　in　situ　nuclear　magnetic　resonance,　in　situ　attenuated　total　reflectance　infrared,　and　theoretical　calculation.　Moreover,　NDN　catalysts　exhibit　a　good　catalytic　feasibility　on　the　synthesis　of　important　natural　products　(e.g.,　intermediates　of　vitamin　E　and　K3)　from　phenol　oxidation.　Copyright　©　2019　American　Chemical　Society.