Hexagonal boron nitride (h-BN) catalyst has recently been reported to be highly selective in oxidative dehydrogenation of propane (ODHP) for olefin production. In addition to propene, ethylene also forms with much higher overall selectivities to C2-products than to C1-products. In this work, we report that the reaction pathways over the h-BN catalyst are different from the V-based catalysts in ODHP. Oxidative coupling reaction of methyl, an intermediate from the cleavage of C─C bond of propane, contributes to the high selectivities to C2-products, leading to more C2-products than C1-products over the h-BN catalyst. This work not only provides insight into the reaction mechanisms involved in ODHP over the boron-based catalysts but also sheds light on the selective oxidation of alkanes such as direct upgrading of methane via oxidative upgrading to ethylene or CH x O y on boron-based catalysts.