Our understanding of the catalyst-free growth of single-walled carbon nanotubes by chemical vapor deposition is limited. Toward improving our knowledge base, we conducted systematic investigations into the initial preparation of C(60) fullerenes as nucleation precursors for single-wall and even double-wall carbon nanotube fabrication. The role of the dispersing media is shown to be crucial and is related to the initial fullerene cluster size. Oxygen-based groups, in particular, epoxy groups, are shown to be vital prior to actual growth. Moreover, the presence of oxygen groups during the growth phase is necessary for tube development. We also demonstrate the possibility of fabricating the tubes in crossbar configurations with bespoke crossing angles in a single synthesis step, unlike other routes which require at least two synthesis steps. The systematic studies significantly advance our understanding of the growth mechanisms involved in all-carbon catalyst-free growth of single- and double-walled carbon nanotubes.