Surface structural engineering has been widely applied to improve the electrochemical performances of LiCoO2 cathodes, especially for applications at high operation voltages (>4.4 V vs. Li) and elevated working temperature (>= 50 degrees C). In this report, Al2O3 layer with an average thickness of 8 nm was firstly obtained on the LiCoO2 surface, and then was transformed into LiAlO2/LiCo(1-x)AlxO(2) double-layers by a facile heating treatment. This novel double-layers structure was clearly presented by high resolution transmission electron microscopy (HRTEM) and depth profile of X-ray photoelectron spectroscopy (XPS). Due to the chemical/electrochemical stability of the LiAlO2 layer and high Li thorn conductivity of the LiCo1-xAlxO2 layer, this cathode with hierarchical structure achieved higher capacity and better cycling stability than the Al2O3 coated LiCoO2 cathode at both 25 and 55 degrees C. In addition, this LiAlO2/LiCo1-xAlxO2/LiCoO2 cathode maintained the capacity of 178.1 mA h g(-1) (73% capacity retention) after 500 cycles (3.0-4.5 V, 1C), which is very promising to be used in severe operation conditions such as high temperature and voltage. (C) 2018 Elsevier Ltd. All rights reserved.