Atomically thin hexagonal boron nitride (hâBN) is an emerging star of 2D materials. It is taken as an optimal substrate for other 2Dâmaterialâbased devices owing to its atomical flatness, absence of dangling bonds, and excellent stability. Specifically, hâBN is found to be a natural hyperbolic material in the midâinfrared range, as well as a piezoelectric material. All the unique properties are beneficial for novel applications in optoelectronics and electronics. Currently, most of these applications are merely based on exfoliated hâBN flakes at their proofâofâconcept stages. Chemical vapor deposition (CVD) is considered as the most promising approach for producing largeâscale, highâquality, atomically thin hâBN films and heterostructures. Herein, CVD synthesis of atomically thin hâBN is the focus. Also, the growth kinetics are systematically investigated to point out general strategies for controllable and scalable preparation of singleâcrystal hâBN film. Meanwhile, epitaxial growth of 2D materials onto hâBN and at its edge to construct heterostructures is summarized, emphasizing that the specific orientation of constituent parts in heterostructures can introduce novel properties. Finally, recent applications of atomically thin hâBN and its heterostructures in optoelectronics and electronics are summarized.