Carbon spheres with size of 50-300 nm were synthesized via a solvent-thermal reaction with calcium carbide and chloroform as reactants in a sealed autoclave. The morphologies and microstructures of carbon spheres before and after high temperature treatment (HTT) were characterized by X-ray diffractometry (XRD), scanning electronic microscopy (SEM), energy diffraction spectroscopy (EDS), and transmission electron microscopy (TEM). The formation mechanism of carbon spheres was discussed. The results indicate that the carbon spheres convert to hollow polyhedron through HTT. Carbon spheres are composed of entangled and curve graphitic layers with short range order similar to cotton structure, and carbon polyhedron with dimension of 50-250 nm and shell thickness of 15-30 nm. The change of solid spheres to hollow polyhedron with branches gives a new evidence for formation mechanism of hollow carbon spheres.