Si has the highest theoretical capacity among all known anode materials, but it suffers from the dramatic volume change upon repeated lithiation and delithiation processes. To overcome the severe volume changes, Si nanoparticles were first coated with a polymer-driven carbon layer, and then dispersed in a CNT network. In this unique structure, the carbon layer can improve electric conductivity and buffer the severe volume change, whereas the tangled CNT network is expected to provide additional mechanical strength to maintain the integrity of electrodes, stabilize the electric conductive network for active Si, and eventually lead to better cycling performance. Electrochemical test result indicates the carbon-coated Si nanoparticles dispersed in CNT networks show capacity retention of 70% after 40 cycles, which is much better than the carbon-coated Si nanoparticles without CNTs.