In　heterogeneous　catalysis,　oxygen　vacancies　of　metal　oxides　play　a　key　role　by　modulating　properties　of　coordination,　electron　states,　electrical　conductivity,　and　surface　property.　However,　the　investigation　of　oxygen　vacancies　in　nonmetal　oxides　and　their　catalytic　applications　have　rarely　been　reported.　Here,　we　present　oxygen　vacancies-rich　BPO4　hollow　spheres　covered　by　few-layer　hexagonal　boron　nitride　(BN)　with　a　sandwich-like　structure　(BN@BPO4@BN)　through　an　in-situ　growth　method.　The　as-prepared　catalyst　showed　better　catalytic　activity　and　higher　selectivity　than　that　of　commercial　BN　in　the　oxidative　dehydrogenation　of　propane　to　propene　because　of　the　synergetic　effect　between　oxygen　vacancies-rich　BPO4　and　h-BN.　Oxygen　vacancies　increase　the　adsorption　amount　of　propane　and　the　confined　space　at　the　interface　of　BN　and　BPO4　weakens　the　adsorption　of　propene,　beneficial　for　the　recycle　of　active　sites.　Moreover,　the　confined　space　and　oxygen　vacancies　result　in　the　transformation　of　reaction　kinetic　model.