A unique hierarchically nanostructured composite of Si nanoparticles (Si NPs) embedded in a three-dimensional (3D) carbon nanotube (CNT)/graphene sheet (GS) matrix (Si@CNT/GS) is fabricated by freeze-drying and thermal reduction. In this novel nanostructured composite, since the intertwined elastic CNTs effectively disperse the Si NP anode material and provide extra physical connections between Si NPs and the surrounding 3D conductive matrix, the interconnected 3D CNT/GS matrix can serve to buffer the volume change of the Si NPs during cycling while simultaneously enhance the electrical conductivity of the overall electrode. As a result, Si@CNT/GS nanocomposite exhibits a high reversible capacity of 1362 mAh·g -1 at 500 mA·g -1 over 500 cycles, and an excellent rate capability of 504 mAh·g -1 at 8400 mA·g -1 , considerably improving the battery performance compared with those electrodes made from Si@graphene nanocomposites, thus exhibiting great potential as an anode composite structure for lithium storage. Copyright © 2017 VBRI Press.