Phase transitions and the related phase identifications for the layered rhombohedral Li(Ni1/3Co1/3Mn1/3)O2 with different electrochemical experience have been studied by transmission electron microscopy. The preliminary results show the existence of two types of new phases: spinel and rocksalt phases. The phase transition from rhombohedral to spinel phase happened only after formation and distributed on the surface of the particles, while the layered rhombohedral structure was kept inside.Another rocksalt phase was also identified on the surface of cycled sample which may getting thicker with the number of cycles. The phase transition from layered rhombohedral phase to spinel and then the rocksalt phase may explain the increased DCR and the capacity loss during cycling and storage. The twinning domains of layered rhombohedral phase were also found on the surface of the crystallite after 60°C storage at discharged state. The twinning domains on the surface may block the Li+ diffusion  space between the layers of the bulk, and thus make contribution to the DCR increase during storage.