A greatly improved synthesis of C-36, obtained as its hydrides C36H4 and C36H6 and oxyhydrides C36H4O and C36H6O, via a high-temperature laser vaporization (laser-furnace) method and the conventional DC arc-discharge method is reported. We have found that doping metal catalysts such as Ni/Co or Ni/N into the laser target graphite rod or the DC are-discharge electrode, respectively, significantly enhanced the production of C36 species; the methods have been known for efficient production methods of single-wall carbon nanotubes (SWNTs). The results suggest that the catalytic formation of C36 species and SWNTs is closely related with each other in their early stage of formation. Furthermore, a molecular C36H6 gives C18H3 (m/z = 219) as a magic fragment upon desorption/ionization. By using a high-performance liquid chromatography (HPLC), C36H6 was purified (99%) in milligram quantity for the first time. The purified C36H6 exists as a cluster-assembled material such as oligomers or clusters in the solid state, not as a molecular crystal such as C-60.