High-voltage LiCoO2 has been revisited to improve the energy density of lithium ion batteries. LiCoO2 can deliver the reversible capacity of about 200 mA h g−1 when the upper cut-off voltage increases to 4.55 V (vs. Li/Li+). However, the high upper cut-off voltage causes the severe failures of LiCoO2 such as structural degradation, electrolyte decomposition, and Co dissolution. Various surface-modified LiCoO2 materials have been introduced to suppress electrolyte decomposition and Co dissolution, thereby leading to the improved electrochemical performance. Most of the coated LiCoO2 materials are obtained through a conventional coating process such as sol-gel synthesis, which is complex and high-cost. In this paper, the in situ electrochemical coating method is introduced as a simple and low-cost coating process, where the electrolyte additive of Mg salts is electrochemically decomposed to form a MgF2-based coating layer on the LiCoO2 surface. LiCoO2 electrochemically coated with MgF2 suppresses Co dissolution in electrolytes, resulting in excellent electrochemical performance such as high reversible capacity of 198 mA h g−1 and stable cycle performance over 100 cycles in the voltage range between 3 and 4.55 V (vs. Li/Li+) at 45 °C. The formation mechanism of MgF2 is also demonstrated through ex situ XPS and XANES analyses.