Hollow resorcinol-formaldehyde (RF) aerogel spheres were synthesized by interfacial polymerization of resorcinol and formaldehyde monomers with NaOH as a catalyst. Commercial hollow polystyrene spheres were used as catalyst storage materials and templates in the synthesis. Hollow carbon acrogel spheres were prepared by carbonization of the RF aerogel spheres at a high temperature under a nitrogen atmosphere. The processing procedures and the conditions of the structures of hollow carbon spheres were Studied.