The initial stages of BN growth on Ni(100) have been studied by means of thermal desorption mass spectrometry (TDS), X-ray photoelectron spectrometry (XPS), and low-energy electron diffraction (LEED). TDS and XPS measurements have shown that condensed multilayers of B 2 H 6 and NH 3 coadsorbed on Ni(100) at low temperature will react during heating to form sub-monolayer coverages of BN. This reaction was observed to occur in the absence of electron irradiation, indicating that the reaction between B 2 H 6 and NH 3 to form BN on the Ni(100) surface can be thermally activated. Under low-pressure (< 10 - 6 Torr) growth conditions, exposing Ni(100) to both B 2 H 6 and NH 3 simultaneously at 950 K results in self-limiting BN growth. XPS measurements of the BN films grown at low pressure indicate the formation of roughly one monolayer of BN on the Ni(100) surface. LEED of the BN film grown at 950 K was found to produce a (1 7) diffraction pattern. This diffraction pattern is consistent with the formation of a monolayer of strained hexagonal BN on the Ni(100) surface. The BN monolayer on the Ni(100) surface was found to be quite stable in atmosphere, with no detectable oxidation after exposure to atmosphere for several days. Subsequent growth of BN by MOCVD (at 76 Torr) on the BN-covered Ni(100) surface leads to further growth of hexagonal BN overlayers.