In this work, 4H-SiC substrates intentionally misoriented from the (0001) plane toward [1-100] direction are shown to eliminate rotational twinning in icosahedral boron arsenide (B12As2, abbreviated here as IBA) epitaxial films. Previous studies of IBA on other substrates, including (100), (110), (111) Si and (0001) 6H-SiC, produced polycrystalline and twinned epilayers. Comparisons of IBA on on-axis and off-axis c-plane 4H-SiC by synchrotron white beam x-ray topography (SWBXT), and high resolution transmission electron microscopy (HRTEM) confirm the single crystalline and much higher quality of the films on the latter substrates. Furthermore, no intermediate layer between the epilayer and substrate was observed for IBA on off-axis 4H-SiC. Steps formed on the off-axis 4H-SiC substrate surface before deposition cause the film to adopt a single orientation, a process that is not seen with substrates with either no misorientation, or those tilted toward the [11-20] direction. This work demonstrates that c-plane 4H-SiC with 7° offcut toward (1-100) is potentially a good substrate choice for the growth of high-quality, untwinned B12As2 epilayers for future device applications.