The effects of precipitation pH values on the microstructural characteristics of nickel hydroxide materials synthesized by a chemical precipitation method have been studied. The relationship between structural characteristics and electrochemical activity of nickel hydroxide was also examined. The structural characteristics of the synthesized β-Ni(OH)2, such as degree of crystallinity, crystalline lattice disorders, crystallite size and crystal growth orientation were strongly related to the pH values of the chemical precipitation reaction. The amounts of SO4 2−, CO3 2− and H2O adsorbed in crystals, and the thermal stability of the β-Ni(OH)2 also depended on the pH. Under relatively high pH values, the synthesized nickel hydroxide materials possessed a reduced crystallite size and lower thermal stability, more crystalline defects and a higher Ni composition. All these characteristics were likely to improve the electrochemical activity of nickel hydroxide.