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, benefiting the recycle of active sites. Moreover, the confined space and oxygen vacancies result in the transformation of reaction kinetic model.