Elimination of degenerate epitaxy in the growth of icosahedral boron arsenide (B12As2, abbreviated as IBA) was achieved on m-plane 15R-SiC substrates and 4H-SiC substrates intentionally misoriented by 7 degrees from (0001) towards [1-100]. Synchrotron white beam x-ray topography (SWBXT) revealed that only single orientation IBA was present in the epitaxial layers demonstrating the absence of twin variants which dominantly constitute the effects of degenerate epitaxy. Additionally, low asterism in the IBA diffraction spots compared to those grown on other SiC substrates indicates a superior film quality. Cross-sectional high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM) both confirmed the absence of twins in the IBA films and their high quality. The ease of nucleation on the ordered step structures present on these unique substrates overrides symmetry considerations that drive degenerate epitaxy and dominates the nucleation process of the IBA.