Abstract Atomically thin hexagonal boron nitride films were grown on both the top and bottom surfaces of a polycrystalline Co or Ni film by annealing a Co (Ni)/amorphous boron nitride/SiO₂ structure in vacuum. This method of growing hexagonal boron nitride is much simpler than other methods, such as thermal chemical vapour deposition. B and N atoms diffuse through the metal film, although N is almost completely insoluble in both Co and Ni, and precipitation occurs at the topmost surface. The mass transport is considered to be caused by grain boundary diffusion.