We developed the novel electrode which enables fine control of overpotential by exploiting surface segregation that is the enrichment of one component at the surface of binary alloy. To realize this approach, we controlled the proportion of Si with low Li diffusivity at the surface by annealing the SiGe nanowire in H2 environment at various temperatures. The resulting SiGe nanowires annealed at 850 °C exhibited high reversible capacity (> 1031 mA·h·g-1), and long cycle life (400 cycles) with high capacity retention (89.0 %) at 0.2 C. This superior battery performance is attributed to the remaining unlithiated part acting as support frame to prevent pulverization of anode material, which results from the fine-tuning of overpotential by controlling the degree of Si segregation.