This work presents a method of enhancing the kinetics of the interfacial reaction using 1,3,5-trifluorobenzene (TFB) which is used as an electron acceptor due to its locally biased polarity and as a source of rearranging the layer of the electrolyte around LiCoO2 electrode, not a SEI layer source. The full cells with TFB show a decrease in irreversible capacity loss during the first charge-to-discharge process, regardless of the SEI layer formation, and also show better discharge properties even at high rate conditions. The charge transfer resistance (R ct) of the LiCoO2 half cell with TFB shows the smaller resistance than that of the TFB free half cell, and the activation energy calculated from the R ct was 24.7kJ/mol for the TFB free half cell and 19.3kJ/mol for the half cell with TFB. In addition, the film resistance of the half cell with TFB shows higher value when the temperature is below 283K. Since R ct is related to the transfer resistance of the solvated Li+ ions on the surface of the LiCoO2 electrode, it will help design the electrolyte to improve the transfer velocity of Li+ ions around the cathode electrode for high power Li ion battery.