A novel polyvinyl alcohol (PVA) hydrogel method is developed to synthesize Si/CNT/C composites. The Si nanoparticles and CNTs are ‘position’ locked up by PVA hydrogel in a simple aqueous solution process, and then the Si-CNT-PVA hydrogel has pyrolyzed to form Si/CNT/C composites. In this unique structured Si/CNT/C composites, the CNTs form a porous network acting both as conductive agent for electron transfer and buffer space to accommodate huge Si volume change during lithiation/delithiation process, while the coating layer of carbon carbonized from polyvinyl alcohol (PVA) hydrogel is conducive to stabilize the interweaved composite structure. The complex structures of Si/CNT/C composites and their electrochemical properties are presented in this paper. The Si/CNT/C composites exhibit an initial reversible capacity of nearly 800 mAhg−1, an excellent capacity retention of 97.1% after 100 cycles at the rate of 0.1 C, and high capacity retention even at high current rate.