Functional electrolytes with additives are one of the key materials which affect the electrochemical performance of the Li-ion batteries such as energy density, power density and cycling performance. This paper gives a short overview of recent works on some new functional electrolyte additives involve P/N/F/S-containing and new type of lithium salts. The insights of working mechanism of these additives are summarized. The newly progress of in situ spectroscopic techniques and theoretical tools to characterize the composition, structure and growth of solid electrolyte interfaces (SEIs) are also briefly reviewed.