This invention relates to LiCoO2 doped with Zr and P, positive material of Li ionic secondary cells and its preparation method characterizing that the chemical formula is: LiZrxCo(1-x-y)PyO2, in which, it is a laminated structure, and x=0.001-0.003, y=0.02-06, the preparation steps are as folow: 1, mixing Co3O4, CoCO3 or CoC2O4 with Li2CO3 or LiOH in the atomic ratio of Li and Co(0.9801.05) :1.00, 2, baking it for 6-24h under 600-1000deg.C, 3, crushing LiCoO2 to particles of 6-15mum, 4, mixing the LiCoO2 and water 1-3times weight into pulp, 5, adding ZrNO3 and phosphate at the same time, 6, spraying and drying it, 7, baking it for 4-12h under 600-1000deg.C, 8, crushing the doped LiCoO2 to particles of 6-15mum.