The influences of LiBF4, LiClO4, lithium bis(oxalato) borate (LiBOB), LiPF6 with VC and without VC, and the mixed electrolytes composed of different ratios of LiBOB and LiPF6 or LiClO4 on the electrochemical properties of Si/graphite/disordered carbon (Si/G/DC) composite electrode were systematically investigated by constant current charge–discharge and electrochemical impedance spectra (EIS) techniques. Scanning electron microscopy (SEM) was used to observe the change of electrodes in morphology after given cycle numbers. X-ray photoelectron spectroscopy (XPS) was employed to understand the influences of different mixed electrolytes on the composition of SEI layers. The results showed that Si/G/DC composite electrode in the mixed electrolytes presented better electrochemical performance than in single electrolyte. The compactness and compositions of SEI layers intensively influenced the cycle performance of Si/G/DC composite materials. LiBOB and additive VC had a good synergistic effect on the formation of the dense SEI layers. In particular, Si/G/DC in 0.5M LiBOB+0.38M LiPF6 electrolytes containing VC exhibited a high reversible capacity and excellent cycle performance.