A BP layer was grown on the (0 0 0 1)-surface of 6H-type hexagonal SiC substrate by atmospheric-pressure metalorganic VPE, and crystallographic feature of the resultant BP/SiC hetero-structure was evaluated by transmission electron microscopy (TEM) and transmission electron diffraction (TED). Analysis of the TED patterns from the hetero-structure gave the following epitaxial relationship: (0 0 0 1), < a-axes >-SiC // (1 1 1), < 1 1 0 >-BP. Extra diffraction spots in the TED pattern indicated the presence of { 1 1 1 }-twins in the (1 1 1)-BP layer. High-resolution TEM observation also revealed the presence of random texture which involved irregular configuration of atomic planes in the (1 1 1)-BP layer at the hetero-interface with the (0 0 0 1)SiC. The MOCVD-grown (1 1 1)-BP layer was deduced to develop on the (0 0 0 1)-SiC, accompanying the formation of the (1 1 1)-twins and of the random texture at the interface with the (0 0 0 1)-SiC. (c) 2004 Published by Elsevier B.V.