Borocarbonitride　(BCN)　catalysts,　boasting　multiple　redox　sites,　have　shown　considerable　potential　in　alkane　oxidative　dehydrogenation　(ODH)　to　olefin　molecules.　However,　their　catalytic　efficiency　still　lags　behind　that　of　leading　commercial　catalysts,　primarily　due　to　the　limited　reactivity　of　oxygen　functional　groups.　In　this　study,　a　groundbreaking　hybrid　catalyst　is　developed,　featuring　BCN　nanotubes　(BCNNTs)　encapsulated　with　manganese　(Mn)　clusters,　crafted　through　a　meticulous　supramolecular　self-assembly　and　postcalcination　strategy.　This　novel　catalyst　demonstrates　a　remarkable　enhancement　in　activity,　achieving　30%　conversion　and　≈100%　selectivity　toward　styrene　in　ethylbenzene　ODH　reactions.　Notably,　its　performance　surpasses　both　pure　BCNNTs　and　those　hosting　Mn　nanoparticles.　Structural　and　kinetic　analyses　unveil　a　robust　interaction　between　BCNNTs　and　the　Mn　component,　substantially　boosting　the　catalytic　activity　of　BCNNTs.　Furthermore,　density　functional　theory　(DFT)　calculations　elucidate　that　BCNNTs　encapsulated　with　Mn　clusters　not　only　stabilize　key　intermediates　(─B─O─O─B─)　but　also　enhance　the　nucleophilicity　of　active　sites　through　electron　transfer　from　the　Mn　cluster　to　the　BCNNTs.　This　electron　transfer　mechanism　effectively　lowers　the　energy　barrier　for　─C─H　cleavage,　resulting　in　a　13%　improvement　in　catalytic　activity　compared　to　pure　BCNNTs.　©　2024　Wiley-VCH　GmbH.