Double-shelled C/SiO2 hollow microspheres with an outer nanosheet-like silica shell and an inner carbon shell were reported. C/SiO2 aerosol particles were synthesized first by a one-step rapid aerosol process. Then the solid silica layer of the aerosol particles was dissolved and regrown on the carbon surface to obtain novel C/SiO2 double-shelled hollow microspheres. The new microspheres prepared by the facile approach possess high surface area and pore volume (226.3 m(2) g(-1), 0.51 cm(3) g(-1)) compared with the original aerosol particles (64.3 m(2) g(-1), 0.176 cm(3) g(-1)), providing its enhanced enzyme loading capacity. The nanosheet-like silica shell of the hollow microspheres favors the fixation of Au NPs (C/SiO2/Au) and prevents them from growing and migrating at 500 C. Novel C/C and C/Au/C (C/Pt/C) hollow microspheres were also prepared based on the hollow nanostructure. C/C microspheres (482.0 m(2) g(-1), 0.92 cm(3) g(-1)) were ideal electrode materials. In particular, the Au NPs embedded into the two carbon layers (C/Au/C, 431.2 m(2) g(-1), 0.774 cm(3) g(-1)) show a high catalytic activity and extremely chemical stability even at 850 C. Moreover, C/SiO2/Au, C/Au/C microspheres can be easily recycled and reused by an external magnetic field because of the presence of Fe3O4 species in the inner carbon shell. The synthetic route reported here is expected to simplify the fabrication process of double-shelled or yolk-shell microspheres, which usually entails multiple steps and a previously synthesized hard template. Such a capability can facilitate the preparation of various functional hollow microspheres by interfacial design.