Carbon　materials　have　stimulated　tremendous　interest　in　oxidative　dehydrogenation　(ODH)　of　alkane　to　olefin　molecules　at　low　temperature.　Unfortunately,　its　further　development　has　been　seriously　hindered　due　to　the　unsatisfactory　catalytic　performance.　To　tackle　these　challenges,　nitrogen　and　phosphorus　codoped　hollow　carbon　prisms　(NPC)　are　designed　with　controllable　surface　functional　groups　through　supramolecular　pre-assembly　and　substitution　reaction　from　guanine　and　hexachlorotriphosphazene.　The　resultant　catalysts　can　achieve　both　high　catalytic　activity　(63　%　conversion)　and　styrene　selectivity　(90　%)　in　ODH　of　ethylbenzene,　outerperforming　previous　reported　carbon-based　catalysts.　Structural　characterizations,　kinetics　measurements　and　theoretical　results　unravel　that　nitrogen　doping　can　promote　nucleophilicity　of　–C[dbnd]O,　thus　improving　the　catalytic　activity.　The　phosphorus　doping　not　only　changes　reaction　rate-determining　step　from　activation　of　O2　in　N-doped　carbon　to　activation　of　–C–H　bond　of　EB　in　N,P-codoped　carbon,　but　also　inhibits　the　formation　of　electrophilic　oxygen　species,　which　enhances　selectivity　of　styrene.　The　current　work　provides　a　facile　strategy　for　preparation　of　functional　NPC　catalyst　and　physical–chemical　insights　on　the　structure–activity　relationship　of　NPC　catalysts,　paving　the　way　for　further　development　of　the　highly　efficient　non-metallic　catalytic　systems.　©　2024　Elsevier　B.V.