Porous silicon nanowire is fabricated by a simple electrospinning process combined with a magnesium reduction; this material is investigated for use as an anode material for lithium rechargeable batteries. We find that the porous silicon nanowire electrode from the simple and scalable method can deliver a high reversible capacity with an excellent cycle stability. The enhanced performance in terms of cycling stability is attributed to the facile accommodation of the volume change by the pores in the interconnect and the increased electronic conductivity due to a multi-level carbon coating during the fabrication process.