Boron sub-arsenide, B12As2, is based on twelve-atom clusters of boron atoms and two-atom As–As chains. By contrast, SiC is a tetrahedrally bonded covalent semiconductor. Despite these fundamental differences, the basal plane hexagonal lattice constant of boron sub-arsenide is twice that of SiC. This coincidence suggests the possibility of heteroepitaxial growth of boron sub-arsenide films on properly aligned SiC. However, there are a variety of incommensurate alignments by which heteroepitaxial growth of B12As2 on (0001) 6H–SiC can occur. In this study, we first used geometrical crystallographic considerations to describe the possible arrangements of B12As2 on (0001) 6H–SiC. We identified four translational and two rotational variants. We then analyzed electron backscattered diffraction and transmission electron microscopy images for evidence of distinct domains of such structural variants. Micron-scale regions with each of the two possible rotational alignments of B12As2 icosahedra with the SiC surface were seen. On a finer length scale (100–300 nm) within these regions, boron-rich boundaries were found, consistent with those between pairs of the four equivalent translational variants associated with a two-to-one lattice match. Boron-carbide reaction layers were also observed at interfaces between SiC and B12As2.