Abstract: The selective oxidation of primary alcohols represents a premier route for the synthesis of aldehydes as intermediates of multiple commercial fine chemicals such as drugs and perfumes. In particular, catalytically selective oxidation of primary alcohol in use of oxygen is of great interest, owning to its high efficiency, solvent-free, and easy separation. As such, choosing this route to pursue desired atomic economy has been an essential topic of common concern in both academic and industrial circles in recent years. Boron nitride with graphite like structure is a new catalyst developed in recent years, which has the characteristics of stability and good thermal conductivity. In this contribution, three kinds of boron nitride (BN) with different structural characteristics were used as carriers to support Au nano metal for selective oxidation of benzyl alcohol. It is found that the crystallinity and specific surface area of the carriers have a great influence on the size of active phase Au. The specific surface area of ​​Au/BN₅₀₀ is four times higher than those of the Au/BN₆₀₀ and Au/BN₇₀₀. Compared with Au/BN₇₀₀, Au/BN₅₀₀ catalyst has better dispersion and smaller particle size (13 vs. 3.2 nm). The catalytic activity of Au/BN₅₀₀ is about twice as much as those of the other two, and about 30% activity is lost within 5 h. The results in this paper provide enriched experimental and theoretical references for rational design and development of novel high-performance boron nitride-based oxidative dehydrogenation catalysts.