Using Ni as catalyst, boron carbonitride (BCN) nanotubes/nanofibres were synthesized from a mixture of N-2, H-2, CH4, and B2H6 by means of plasma-assisted hot filament chemical vapor deposition. The activated Ni catalysts exhibit some preferred crystal orientations at different inlet B2H6 concentrations, such as [011] at 1.0%, [(1) over bar 11] at 1.5%, and [(1) over bar 13] at 2.0%, respectively. Our results imply that Ni catalytic particles play an important role in the formation of the stable phases of BCN nanotubes/nanofibres with different chemical compositions.