Tin-based materials, due to their high theoretical capacity of 994 mAh g-1 are potential candidates which can substitute the commercialized graphite anodes (372 mAh g-1). However, practical usage of pure tin in Li-ion cells has been hampered by the tremendous volume expansion of more than 260% during the lithium insertion/extraction process, resulting in particle pulverization and electrical disconnection from the current collector. In order to overcome this shortcoming, Sn/Cu6Sn5/C composites in this work were prepared by using pulsed wire explosion in a liquid medium and subsequently in situ polymerization. For comparison, Sn/C composite without tin-copper chemical compounds are also fabricated under a similar process. The Sn/Cu6Sn5/C and Sn/C composites were used as anodes for lithium-ion batteries. The Sn/Cu6Sn5/C composite anode showed good cyclability (scalability) and was maintained up to a capacity of 430 mAh g-1 after 100 cycles at 1 C-rate. The rate capability of the Sn/Cu6Sn5/C composite anode also showed higher performance (280 mAh g-1) than that (200 mAh g-1) of Sn/C composite at the 5 C-rate.