Tin-based electrodes have attracted much attention because of their potential to offer high energy and power density while maitaining excellent cycling stability. Here we report our findings from the rational design and synthesis of a high-performance Cu6Sn5@SnO2–C electrode, a tin-based anode with a unique core/shell structure consisting of a tin–copper intermetallic (Cu6Sn5) core and a tin dioxide (SnO2)/carbon (C) shell. The hybrid structure was synthesized by a simple and cost-effective two-step process. When used as an electrode, the Cu6Sn5@SnO2–C hybrid nanocomposite demonstrated a reversible capacity of 619mAh/g after 500 cycles between 0.05 and 3.0V vs. Li/Li+ at 0.2A/g, with stable capacities of ~300mAh/g from the reversible conversion reaction of SnO2 in a potential range of 1.1–2.0V. Results suggest that the maximum volume change of the Cu6Sn5@SnO2–C electrode during cycling was relatively small (~12.7%) so that the Cu6Sn5 core components and the core/shell structure remained relatively stable over many cycles, leading to significantly enhanced reaction reversibility and cycling stability.