Formation of carbon nanocapsules with various clusters (SiC, Au, Fe. Co. Ge. and GeO2) by polymer pyrolysis was investigated, and nanocapsules with SiC and Au nanoparticles were produced by thermal decomposition of polyvinyl alcohol at −500°C in Ar gas atmosphere. The formation mechanism of nanocapsules and a structural model for the nanocapsule/SiC interface were proposed. In addition, carbon clusters were formed at the surface of carbon nanocapsules, and carbon onions were produced by electron irradiation of amorphous carbon produced from polyvinyl alcohol. The present work indicates that the pyrolysis of polymer materials with clusters is a useful fabrication method for the mass-production of carbon nanocapsules and onions at low temperatures compared to the ordinaly are discharge method.