Thiophene derivatives (THs) are examined as novel functional additives for improving the cycling performance of high-voltage LiCoO2. Our investigation reveals that 2,2′-Bithiophene (2TH) and 2,2′:5′,2′′-Terthiophene (3TH) can be electrochemically polymerize prior to the electrolyte solvent decomposition to form a protective layer of conducting polymer film on the cathode surface, which blocks off severe electrolyte decomposition at high voltages and, therefore, improves the cycling stability of high voltage LiCoO2 cathode. After 100 cycles at a high cutoff voltage of 4.4V, the discharge capacity retention is 50% in the base electrolyte, in contrast, the LiCoO2 cathode cycled in the electrolyte containing 0.1 wt% 3TH displays a high capacity retention of 84.8% at 0.25C rate. This work demonstrates that these thiophene derivatives have considerable potential as functional additives for the applications in high-voltage lithium-ion batteries.