Lithium cobalt oxide, as a popular cathode in portable devices, delivers only half of its theoretical capacity in commercial lithium-ion batteries. When increasing the cut-off voltage to release more capacity, solubilization of cobalt in the electrolyte and structural disorders of lithium cobalt oxide particles are severe, leading to rapid capacity fading and limited cycle life. Here, we show a class of ternary lithium, aluminum, fluorine-modified lithium cobalt oxide with a stable and conductive layer using a facile and scalable hydrothermal-assisted, hybrid surface treatment. Such surface treatment hinders direct contact between liquid electrolytes and lithium cobalt oxide particles, which reduces the loss of active cobalt. It also forms a thin doping layer that consists of a lithium-aluminum-cobalt-oxide-fluorine solid solution, which suppresses the phase transition of lithium cobalt oxide when operated at voltages >4.55 V.