The hexagon single-crystal Co(OH)2 nanoplates, which obtained by hydrothermal synthesis method, can be transformed to the porous single-crystal Co3O4 nanoplates after the heat treatment above 300 °C in air. Electrochemical tests show that the lithium storage performances of porous Co3O4 nanoplates are influenced more closely to its structural aspects than its morphology and size factors, which can be controlled by changing the heat treatment temperature. When the heat treatment temperature is increased to 500 °C, the robust single-crystal Co3O4 nanoplates with relatively large mesoporous size and low specific surface area can be obtained via the long-range atom diffusion at high temperature, which exhibit low initial irreversible capacity, superior cycling performance and excellent rate capability.