Hexagonal boron nitride (h-BN) is a two-dimensional material with high thermal conductivity, excellent thermal stability and chemical stability. These properties have great potential as the dielectric layers in high performance electronic and optoelectronic devices. In this report, boron nitride was grown on the Ni/SiO 2 /Si substrates by plasma-assisted molecular beam epitaxy (PA-MBE). During the growth of boron nitride, we used the reflection high-energy electron diffraction (RHEED) mounted in ULVAC PA-MBE system to observe the surface conditions. After the growth, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed to characterize boron-nitride. The surface morphology of boron nitride on poly-crystalline Ni was determined by using filed-emission scanning electron microscopy (FE-SEM). Meanwhile, we changed the temperatures of boron K-cell (1200 or 1300 °C) to modify the flux of B atoms for the growth of boron nitride. Raman spectra show a peak of boron nitride at 1380 cm −1 and the peak intensity of BN is higher at the cell temperature as 1300 °C. The results of XPS for the chemical composition of boron nitride also confirmed with Raman data. In summary, boron nitride was successfully grown on the poly-crystalline Ni films by PA-MBE system.