Formation process of nanosized cap structures on a thermally treated 6H-SiC(000-1) substrate was investigated using atomic-resolution ultrahigh-vacuum scanning tunneling microscopy (UHV-STM). After formation of clusters of carobon particles 1-2 nanometer in diameter at 1150°C, these nanoparticles merged, forming nanosized cap structures. Hexagonal carbon networks, partly composed of pentagons, were clearly observed on the surface of the cap structures for a sample annealed above 1200°C. A model for the formation of carbon nanocaps on 6H-SiC(000-1) was proposed.