A sol–gel route has been used to synthesize close-packed SnO2 nanocrystals anchored on amorphous silica as a potential anode material for lithium-ion battery. The materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR, transmission electron microscopy (TEM) and electrochemical techniques. The electrochemical performance of the SnO2/silica composites shows higher capacity and good cycle stability compared with that of the bare SnO2 electrode. It is believed that the good performance as a stable anode material originates from the unique structure of the close-packed nanocrystalline assemblies and the amorphous porous silica as inactive material to mediate the massive volume expansion and contraction of SnO2 during lithiation and delithiation processes. It has been proved for the first time that the close-packed architecture of SnO2 nanocrystals ensure adequate amount of active component for the lithium storage, resulting in a reasonable lithium storage capability for the present system. On the other hand, the crystalline/amorphous interactions should be one of the most fundamental factors to improve the electrochemical stability of the SnO2/silica hybrid electrode.