Abstract2D hexagonal boron nitride (h‐BN), which has a similar honeycomb lattice structure to graphene, is a promising dielectric material for a wide variety of applications. Herein, the growth of high‐quality and large‐size multilayer h‐BN crystals on Cu foils is reported by chemical vapor deposition (CVD) at atmospheric pressure. The size of an individual isolated hexagonal crystal of h‐BN is about 20 µm, and the thickness is 3 nm. This paper studies the variables that affect h‐BN growth during the process and the microstructure changes during the growth. Through analysis of the thermal and dynamic processes of chemical vapor deposition, relationships are derived between the mass of h‐BN grown in the gas phase and various temperature and pressure factors. This information is used to develop appropriate parameters for commercial copper foil growth. Finally, using optimized conditions, high‐quality h‐BN at high pressure and low gas flow conditions are grown.