As observed, the orientation of the boron carbide films on silicon carbide depends on the surface termination, the temperature, and the residence time. The demonstration of epitaxial growth of r-B4C on 4H-SiC(0001 ̅ ) from 1300 °C supports this, while all films deposited on 4H-SiC(0001) were found to be polycrystalline at the studied temperatures.