Novel nanostructured silicon composites, Si/Poly(3,4-ethylenedioxythiophene) nanowire network (Si/PNW) and Si/(S-doped-carbon nanowire network) (Si/S-CNW), are prepared by a soft-template polymerization of 3,4-ethylenedioxythiophene (EDOT) using sodium dodecyl sulfate (SDS) as surfactant with the presence of Si nanoparticles and a subsequent carbonization of Si/PNW, respectively. The presence of Si nanoparticles in the soft-template polymerization of EDOT plays a critical role in the formation of PEDOT nanowire network instead of 1D nanowire. After the carbonization of PEDOT, the S-doped-carbon nanowire network matrix shows higher electrical conductivity than PNW counterpart, which facilitates to construct robust conductive bridges between Si nanoparticles and provide large electrode/electrolyte interfaces for rapid charge transfer reactions. Thus, Si/S-CNW composite exhibits excellent cycling stability and rate capability as anode material, retaining a specific capacity of 820 mAh g−1 after 400 cycles with a very small capacity fade of 0.09% per cycle.