Abstract In this work, SiO 2 nanoplates with opened macroporous structure on carbon layer (C-mSiO 2 ) have been obtained by dissolving and subsequent regrowing the outer solid SiO 2 layer of the aerosol-based C-SiO 2 double-shell hollow spheres. Subsequently, triple-shell C-mSiO 2 -C hollow spheres were successfully prepared after coating the C-mSiO 2 templates by the carbon layer from the carbonization of sucrose. When being applied as the anode material for lithium-ion batteries, the C-mSiO 2 -C triple-shell hollow spheres deliver a high capacity of 501 mA·h·g − 1 after 100 cycles at 500 mA·g − 1 (based on the total mass of silica and the two carbon shells), which is higher than those of C-mSiO 2 (391 mA·h·g − 1 ) spheres with an outer porous SiO 2 layer, C-SiO 2 -C (370 mA·h·g − 1 ) hollow spheres with a middle solid SiO 2 layer, and C-SiO 2 (319.8 mA·h·g − 1 ) spheres with an outer solid SiO 2 layer. In addition, the battery still delivers a high capacity of 403 mA·h·g − 1 at a current density of 1000 mA·g − 1 after 400 cycles. The good electrochemical performance can be attributed to the high surface area (246.7 m 2 ·g − 1 ) and pore volume (0.441 cm 3 ·g − 1 ) of the anode materials, as well as the unique structure of the outer and inner carbon layer which not only enhances electrical conductivity, structural stability, but buffers volume change of the intermediate SiO 2 layer during repeated charge–discharge processes. Furthermore, the SiO 2 nanoplates with opened macroporous structure facilitate the electrolyte transport and electrochemical reaction.