A mesoporous Co3O4 core/mesoporous silica shell composite with a variable shell thickness of 10-35 nm was fabricated by depositing silica on Co3O4 superlatticed particles. The Brunauer-Emmett-Teller (BET) surface area of the composite with a shell thickness of ca. 2.0 nm was 238.6 m(2)/g, which varied with the shell thickness, and the most frequent pore size of the shell was ca. 2.0 nm. After the shell was eroded with hydrofluoric acid, mesoporous Co3O4 particles with a pore size of ca. 8.7 nm could be obtained, whose BET surface area was 86.4 m(2)/g. It is proposed that in the formation of the composite the electropositive cetyltrimethylammonium bromide (CTAB) micelles were first adsorbed on the electronegative Co3O4 particle surface, which directed the formation of the mesoporous silica on the Co3O4 particle surface. Electrochemical measurements showed that the core/shell composites exhibited a higher discharge capacity compared with that of the bare Co3O4 particles.