We demonstrate hexagonal boron nitride (h-BN) epitaxial growth on Ni(111) substrate by molecular beam epitaxy (MBE) at 890 degrees C. Elemental boron evaporated by an electron-beam gun and active nitrogen generated by a radio-frequency (RF) plasma source were used as the group-III and -V sources, respectively. Reflection high-energy electron diffraction revealed a streaky (1 x 1) pattern, indicative of an atomically flat surface in the ongoing growth. Correspondingly, atomic force microscopy images exhibit atomically smooth surface of the resulting h-BN film. X-ray diffraction characterization confirmed the crystallinity of the epitaxial film to be h-BN, and its X-ray rocking curve has a full-width at half-maximum of 0.61 degrees, which is the narrowest ever reported for h-BN thin film. The epitaxial alignments between the h-BN film and the Ni substrate were determined to be [0001](h-BN)parallel to[111](Ni), [11 (2) over bar0](h-BN)parallel to[(1) over bar 10](Ni), and [(1) over bar 100](h-BN)parallel to[(1) over bar(1) over bar2](Ni). (C) Elsevier B.V. All rights reserved.