Since the successful separation of graphene from its bulk counterpart, two-dimensional (2D) layered materials have become the focus of research for their exceptional properties. The layered hexagonal boron nitride (h-BN), for instance, offers good lubricity, electrical insulation, corrosion resistance, and chemical stability. In recent years, the wide-band-gap layered h-BN has been recognized for its broad application prospects in neutron detection and quantum information processing. In addition, it has become very important in the field of 2D crystals and van der Waals heterostructures due to its versatility as a substrate, encapsulation layer, and a tunneling barrier layer for various device applications. However, due to the poor adhesion between h-BN and substrate and its high preparation temperature, it is very difficult to prepare large-area and denseh-BN films. Therefore, the controllable synthesis of h-BN films has been the focus of research in recent years. In this paper, the preparation methods and applications of h-BN films on III–V compounds are systematically summarized, and the prospects are discussed.