β-Nickel hydroxide microspheres with flakelike nanostructure have been successfully synthesized by a low temperature hydrothermal method at 100 °C for 2 h. The sphere size was about 0.6–1.0 μm. The hierarchical structure was nanoflake and thickness of each nanoflake was about 15 nm. The formation mechanism of β-nickel hydroxide microsphere with flakelike nanostructures was discussed. Their electrochemical properties were also described. The discharge specific capacity is 260 mAh g−1. Because of their unique structures and excellent electrochemistrical properties, the flakelike nanostructures of nickel hydroxide spheres may give a new perspective for applications in the rechargeable batteries.