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In this work, the 2D nanostructured h-BN/WS2 heterojunction was successfully prepared by the hydrothermal method-assisted exfoliation of bulk h-BN and WS2. The morphology and structure of the as-prepared heterojunction were determined by a series of characterization techniques. The mechanism for the formation of the as-prepared heterojunction was proposed. The friction coefficient and wear rate of the as-prepared h-BN/WS2 heterojunction-grease was decreased by 33.9% and 45.9%, respectively, as compared to those of the neat grease.