The　oxidative　dehydrogenation　of　propane　(ODHP)　represents　a　highly　promising　route　for　the　industrial-scale　production　of　propene.　Non-metallic　boron　nitride　(BN)-based　materials,　known　for　their　high　propene　selectivity,　have　emerged　as　next-generation　ODH　catalysts.　However,　the　real　active　sites　on　surfaces　remain　unclear　due　to　the　absence　of　visual　experimental　evidence.　In　this　work,　we　introduce　a　chemical　titration　approach　to　clarify　the　active　centers　of　NaOH　modified　BN　(BN-NaOH)　catalysts　for　ODHP.　The　BN-NaOH　catalyst　demonstrates　outstanding　performance,　achieving　over　90　%　olefin　selectivity　and　a　stable　propane　conversion　of　23.2　%.　Notably,　the　turnover　frequency　(TOF)　for　B-OH　sites　reaching　1.2　h−1,　which　significantly　surpassed　that　of　unmodified　BN　catalysts　(0.6　h−1).　In　situ　diffuse　reflectance　infrared　Fourier　transform　spectroscopy　(DRIFTS)　analysis　revealed　that　the　formation　of　OH-nests　on　the　BN-NaOH　surface　was　primarily　accountable　for　the　enhanced　reactivity.　Moreover,　the　crucial　role　of　these　OH-nests　during　ODHP　was　further　validated　through　selective　chemical　titration　of　B-OH　groups　using　benzoic　anhydride.　©　2025　Elsevier　Ltd