Combining electrodeposition and heat treatment is an effective method to successfully fabricate Cu6Sn5 alloy materials, in which the S2 alloy electrode is electrodeposited at 1.2 A dm-2 current density with uniform and compact morphology. The characterization results show that monoclinic η'-Cu6Sn5 and hexagonal η-Cu6Sn5 phases fabricated at the appropriate current density exhibit excellent electrochemical performance. The optimal Cu6Sn5 alloy anode material boasts not just a significantly high discharge specific capacity of 890.2 mA h g-1 with an initial coulombic efficiency (ICE) of 73.96%, but also achieves an adequate discharge specific capacity of 287.1 after 50 cycles at 100 mA h g-1. Moreover, the electrodeposited Cu6Sn5 alloy materials also possessed a lower transfer resistance of 42.45 Ω and an improved lithium-ion diffusion coefficient of 2.665 × 10-15 cm2 s-1 at the current density of 1.2 A dm-2. Therefore, preparing the Cu6Sn5 alloy thin-film electrode could be a cost-effective and straightforward method by electrodeposition from cyanide-free plating baths to develop anode components suitable for lithium-ion battery applications.