A binder-free three-dimensional (3D) porous Cu6Sn5 anode was prepared for lithium-ion batteries. In this novel approach, tin was deposited by electroless-plating on copper foam which was served as anode current collector as well as the source of copper for Cu6Sn5 alloy formation. With optimized post-treatment condition, Cu6Sn5 alloy with thickness of 1.2μm was formed on the surface of copper foam network. 3D porous Sn–Cu6Sn5 and Cu3Sn–Cu10Sn3–Cu6Sn5 composite anodes were also prepared for comparison. Electrochemical tests showed that 3D porous Cu6Sn5 anode exhibits the best electrochemical performance in terms of specific capacitance and cycleability, which delivers a rechargeable capacity of 404mAhg−1 over 100 cycles.