The β-Co(OH)2 sheets with uniform hexagonal shape were prepared using NaBH4 as the structure directing agent at room temperature. After thermal annealing in air at 450°C for 2h, the as-prepared β-Co(OH)2 sheets were converted into porous Co3O4 with the hexagonal sheet-like morphology (H-Co3O4). The textural properties of the as-prepared samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. The results of lithium storage capability indicate that the H-Co3O4 electrode exhibits excellent cycleability and rate capacity. At a charge/discharge current density of 50mAg−1, a reversible capacity of 914mAhg−1 can be maintained after 40 cycles. When the current density is increased to 1600mAhg−1, a reversible capacity of 800mAhg−1 can be still obtained. The superior electrochemical performance is attributed to the porous 2D structures with a finite lateral size and enhanced open-edges, which facilitate Li-ion and electron diffusion through active materials.