The present invention provides a high-voltage lithium cobaltate positive electrode material, which is a compound structure of a doped lithium cobaltate substrate and a surface coating layer, wherein the general formula of the doped lithium cobaltate substrate is Li1+zCo1-x-yMaxMbyO2, x is more than or equal to 0 and is less than or equal to 0.01, y is more than or equal to 0 and is less than or equal to 0.01, z is more than or equal to -0.05 and is less than or equal to 0.08, Ma is a doped element with unchanged valence, and is at least one selected from Al, Ga, Hf, Mg, Sn, Zn and Zr, Mb is adoped valence-changing element, and is at least one selected from Ni, Mn, V, Mo, Nb, Cu, Fe, In, W and Cr, and the surface coating layer is a high-voltage (more than 4.5 V) positive electrode material. According to the present invention, the element with unchanged valence is doped through substitution, such that the layered structure distortion caused by lithium removing can be minimized; the valence-changing element is subjected to gap doping, such that the Co<3+> oxidation is blended and delayed during the charging; and the surface coating layer has the stable structure at the voltage of more than 4.5 V, can separate the electrolytic solution from the lithium cobaltate substrate, can reduce the side reaction between the electrolytic solution and the lithium cobaltate substrate, can suppress the dissolution of the transition metal, and further can provide electrochemical energy.