Ni-rich mixed metal oxides (LiNi0.80Co0.15Mn0.05O2) as a high capacity cathode material for lithium ion battery are synthesized in two different heat-treatment atmospheres of air and oxygen, respectively. A cell with LiNi0.80Co0.15Mn0.05O2 heat-treated in the oxygen atmosphere shows better electrochemical performance of initial (193.7 mAh/g) and retention (185.2 mAh/g) capacities than a cell with the cathode material heat-treated in the air atmosphere (initial capacity: 185.2 mAh/g and retention capacity: 172.0 mAh/g). In order to find the reasons of the different electrochemical performance, the samples have been characterized in detail by X-ray diffraction and scanning electron microscopy. The structural differences are revealed at the nanometer scale from the experimental works of scanning transmission electron microscopy images mapped with orientation and reliability indices and electron energy loss spectroscopy. The NiO phase of the rock salt structure is considerably developed on the surfaces of the materials in the less oxidative environment of the air atmosphere; this is related to the poor electrochemical performances.