A micro-nano combined composite with Li-Si alloy nano-domains in three-dimensional carbon network was prepared as a novel electrode material. The carbon network constrained the volume contraction and promoted effectively charge transfer of the whole active material. Meanwhile, the abundant interfaces between Li-Si alloy and carbon bound by Li-C ionic bonds, not only enhanced the delithiation at interface but also ensured the structural integrity. The present composite exhibited excellent electrochemical performance. The specific ca-pacity at the first lithiation was as high as 1133 mAh g?1 at a current density of 0.1 A g?1, which is superior to those reported for the core-shell structured nanoparticles. The Coulombic Efficiency at the first cycle was 90.4% and kept stable at more than 99.0% after only 10 cycles. The capacity retention was nearly twice as that of the incompact mixture of Li-Si nanoparticles and carbon. The energy density of the full cell constructed by the present composite and sulfur was evaluated to be 3 times as high as that of the commercial lithium-ion batteries. This work provides a new universal strategy for developing Li-rich anode materials with high combination properties and low cost.