Increasing the charging cutoff voltage of LiCoO2 to 4.6V is significant for enhancing battery density. However, the practical application of Li‖LiCoO2 batteries with a 4.6V cutoff voltage faces significant impediments due to the detrimental changes under high voltage. This study presents a novel bifunctional electrolyte additive, 2-(trifluoromethyl)benzamide (2-TFMBA), which is employed to establish a stable and dense cathode-electrolyte interface (CEI). Characterization results reveal that an optimized CEI is achieved through the synergistic effects of the amide groups and trifluoromethyl groups within 2-TFMBA. The resulting CEI not only enhances the structural stability of LiCoO2 but also serves as a high-speed lithium-ion conduction channel, which expedites the insertion and extraction of lithium ions. The Li‖LiCoO2 batteries with 0.5wt% 2-TFMBA achieves an 84.7% capacity retention rate after enduring 300 cycles at a current rate of 1C, under a cut-off voltage of 4.6V. This study provides valuable strategic insights into the stabilization of cathode materials in high-voltage batteries.