The electrodeposited Sn–O–C composite anode cycling with LiClO4 delivered stable cycle performances showing discharge capacity of 473 mA h g of Sn −1 with 95% of coulombic efficiency at 100th cycle. However, the anode showed poor cycle performances with LiPF6 delivering discharge capacity of 69 mA h g of Sn −1 at 100th cycle with 70% of coulombic efficiency. Electrochemical investigation performed by cyclic voltammetry and differential capacity plots revealed that the Sn–O–C composite cycling with LiPF6 suffered from retarded phase transition reaction between Li and Sn during charge/discharge process. X-ray photoelectron spectroscopy declared the existence of fluorinated-Sn and LiF. Moreover, energy dispersive X-ray spectroscopy found increase in their amount with repeated cycles. The morphologies of the Sn–O–C composite cycled with LiPF6 showed aggregated particles containing the chemical state of fluorinated-Sn and LiF on its surface. Furthermore, the significant pulverization and aggregation of the active material were observed from the Sn–O–C composite cycled by LiPF6 rather than that of LiClO4, which was probably promoted by the generated HF strongly corroding metallic component.