Boroncarbonitrides　(BCNs)　are　recently　developed　new　catalytic　system　for　efficient　oxidative　dehydrogenation　(ODH)　of　alkanes　to　alkenes.　Herein,　a　series　of　novel　hierarchical　BCN　materials　are　synthesized　using　asymmetric　hydrogen　bonds　self　-assembly　between　methylguanidine　and　boric　acid,　along　with　ammonia　deposition.　The　XRD,　S(T)EM,　and　XPS　characterizations　confirm　the　presence　of　ternary　BCN　solid　solution　covered　by　small　serrated　-like　BCN　nanosheets　materials　in　the　2D　plates.　The　unique　hierarchical　structure　and　developed　mesoporosity　of　the　BCN　material　contribute　to　its　outstanding　catalytic　performance.　The　optimal　catalyst　delivers　robust　catalytic　performance　and　long-term　stability　in　the　ODH　of　propane　reaction　with　propylene　and　total　olefin　selectivity　of　74.7%　and　89.7%　at　a　stable　20.4%　propane　conversion,　much　better　than　BCN　sheets　and　h-BN　catalyst.　Results　show　that　the　in　-situ　formation　of　suitable　amounts　of　amorphous　BOX　species　within　the　BCN　structure,　along　with　the　maintenance　of　the　2D　skeleton　at　elevated　temperatures,　is　a　significant　contribution　in　the　enhanced　ODH　reactivity.　Moreover,　density　functional　theory　calculation　also　demonstrates　that　the　presence　appropriate　carbon　content　in　BCN　catalysts　can　significantly　promote　the　ODH　of　propane　reaction.