Proposed is an improvement in a vessel, e.g., crucible, of pyrolytic boron nitride (PBN) used, for example, in the process of molecular beam epitaxy for melting silicon and the like at a high temperature. Different from conventional PBN crucibles used for such a process, in which contamination of high-purity silicon is unavoidable by the reaction of molten silicon with PBN or a thermal decomposition products of boron nitride, the inventive PBN vessel is provided on the surface with a protective coating layer of pyrolytic graphite or a refractory metal such as platinum so as not to cause troubles due to contamination of high-purity silicon melted therein with the crucible materials.