We selected diphenyloctyl phosphate (DPOF) as a flame-retardant and plasticizer, and studied the influence of different amounts of the DPOF additive on the electrochemical performance of lithium-ion batteries. The electrochemical cell performances of the additive-containing electrolytes in combination with a cell comprising an LiCoO2 cathode and mesocarbon microbeads (MCMB) anode were tested in coin cells. The cyclic voltammetry (CV) results showed that the oxidation potential of the electrolyte containing DPOF in the concentration range from 10 to 30wt.% is about 4.75–5.5V versus Li/Li+. In the present work, a DPOF content of 10wt.% in the 1.15M LiPF6/EC:EMC (4:6 by vol.%) electrolyte turned out to be the optimum condition for the improvement of the electrochemical cell performance, due to the decrease of the irreversible capacity during the first cycle and decrease of the charge-transfer resistance after 40 cycles.