The lithium-rich Li[Li0.2Ni0.13Mn0.54Co0.13]O2 nanoplates were synthesized using a molten-salt method. The nanoplates showed an initial reversible discharge capacity of 233 mA·h·g−1, with a fast capacity decay. The morphology and micro-structural change, after different cycles, were studied by a scanning electron microscope (SEM) and transmission electron microscopy (TEM) to understand the mechanism of the capacity decay. Our results showed that the cracks generated from both the particle surface and the inner, and increased with long-term cycling at 0.1 C rate (C = 250 mA·g−1), together with the layered to spinel and rock-salt phase transitions. These results show that the cracks and phase transitions could be responsible for the capacity decay. The results will help us to understand capacity decay mechanisms, and to guide our future work to improve the electrochemical performance of lithium-rich cathode materials.