Hexagonal boron nitride nanosheets (hBNNS) have various promising applications in dielectric and thermal conductive materials. However, in the bottom‐up method, well‐crystallized hBNNS could only be attained at very high temperatures. In this paper, a facile halide‐assisted hydrothermal assembly (HAHTA) method for the low‐temperature synthesis of well‐crystallized hBNNS is prepared. In HAHTA, the lateral growth of hBNNS is enhanced by the halide addition in the precursor, and the dimension reaches several micrometers. In addition, the obtained hBNNS enhance the oxidization resistance of vanadium dioxide (VO2) though the formation of a VO2/hBN composite, which is meaningful in facilitating the potential applications of VO2 as smart phase transition materials.