Hexagonal boron nitride (h-BN), a layer structure material, has gained increasing attentions as a support. Herein, a few-layer h-BN is constructed and employed as an interlayer confining support for heterogenization of phosphotungstic acid (HPW/h-BN). The obtained HPW/h-BN is applied in oxidative desulfurization (ODS) and a similar to 100% of sulfur removal can be achieved. Detailed experiments show that porous structure of h-BN, functioned as confining sites, contributes to the remarkable catalytic activity. Besides, aromatic hydrocarbon and olefin are further applied as chaff interferent in ODS showing no obvious effects, suggesting a promising prospect. This catalyst presents preferable recyclability in ODS, which can be recycled 6 times without noticeable decrease in reactivity. Moreover, the reaction mechanism and resultant are instantly detected by gas chromatography-mass spectrometry. (C) 2016 Elsevier B.V. All rights reserved.