In this study, ester co-solvents and fluoroethylene carbonate (FEC) were used as low-temperature electrolyte additives to improve the formation of the solid electrolyte interface (SEI) on graphite anodes in lithium-ion batteries (LIBs). Four ester co-solvents, namely methyl acetate (MA), ethyl acetate, methyl propionate, and ethyl propionate, were mixed with 1.0 M LiPF6 ethylene carbonate:diethyl carbonate:dimethyl carbonate (1:1:1 by vol%) as the base electrolyte (BE). Different concentrations were used to compare the electrochemical performance of the LiCoO2/ graphite full cells. Among various ester co-solvents, the cell employing BE mixed with 30 vol% MA (BE/MA30) achieved the highest discharge capacity at − 20 °C. In contrast, mixing esters with low-molecular-weight degraded the cell performance owing to the unstable SEI formation on the graphite anodes. Therefore, FEC was added to BE/MA30 (BE/MA30-FEC5) to form a stable SEI layer on the graphite anode surface. The LiCoO2/ graphite cell using BE/MA30-FEC5 exhibited an excellent capacity of 127.3 mAh g− 1 at − 20 °C with a capacity retention of 80.6% after 100 cycles owing to the synergistic effect of MA and formation of a stable and uniform inorganic SEI layer by FEC decomposition reaction. The low-temperature electrolyte designed in this study may provide new guidelines for resolving low-temperature issues related to LIBs, graphite anodes, and SEI layers.