The impedance behavior of silicon nanowire electrodes has been investigated to understand the electrochemical process kinetics that influences the performance when used as a high-capacity anode in a lithium ion battery. The ac response was measured by using impedance spectroscopy in equilibrium conditions at different lithium compositions and during several cycles of charge and discharge in a half cell vs. metallic lithium. The impedance analysis shows the contribution of both surface resistance and solid state diffusion through the bulk of the nanowires. The surface process is dominated by a solid electrolyte layer (SEI) consisting of an inner, inorganic insoluble part and several organic compounds at the outer interface, as seen by XPS analysis. The surface resistivity, which seems to be correlated with the Coulombic efficiency of the electrode, grows at very high lithium contents due to an increase in the inorganic SEI thickness. We estimate the diffusion coefficient of about 2 × 10 -10 cm 2/s for lithium diffusion in silicon. A large increase in the electrode impedance was observed at very low lithium compositions, probably due to a different mechanism for lithium diffusion inside the wires. Restricting the discharge voltage to 0.7 V prevents this large impedance and improves the electrode lifetime. Cells cycled between 0.07 and 0.70 V vs. metallic lithium at a current density of 0.84 A/g (C/5) showed good Coulombic efficiency (about 99%) and maintained a capacity of about 2000 mAh/g after 80 cycles. © 2009 American Chemical Society.