Hydrogen　activation　and　the　consequent　catalytic　hydrogenation　of　nitrobenzene　on　metal-free　catalysts　have　been　an　attractive　alternative　to　traditional　metal-based　catalytic　process.　Here　we　design　a　type　of　B/P　co-doped　nanocarbon　(BPC)　catalyst　via　the　engineering　of　frustrated　Lewis　pairs　(FLPs)　on　nanocarbons.　It　exhibits　excellent　catalytic　activity　with　97%　conversion　and　98%　selectivity　in　hydrogen　assisted　hydrogenation　of　nitrobenzene　to　form　aniline,　which　is　superior　to　that　of　pure　carbon　and　single　B　or　P　doped　carbon　materials.　Structural　characterizations,　kinetic　measurements　and　density　functional　theory　(DFT)　results　indicate　that　Lewis　acid　(＇B＇　center)　and　Lewis　base　(＇P＇　center)　engineered　FLP　sites　on　the　BPC　are　responsible　for　the　formation　of　aniline,　and　the　moderate　P/B　ratio　is　important　in　promoting　the　hydrogenation　activity.　Moreover,　we　put　forward　a　possible　reaction　mechanism　and　point　out　the　key　factors　in　determining　the　reactivity　for　this　reaction.　The　current　work　provides　a　facile　strategy　for　developing　highly　efficient　hydrogenation　catalysts.　©　2022　The　Royal　Society　of　Chemistry.