Spherical Ni(OH)2 particles were prepared by an aqueous solution precipitation route. The structure of spherical Ni(OH)2 was investigated by scanning electron microscopy and transmission electron microscopy and compared with that of traditional Ni(OH)2. The results show that the spherical nickel hydroxide consists of Ni(OH)2 spheres with a reticulate structure of platelet-like, which is almost arranged radially and the crystalline grains intervene and connect with each other to form a three-dimensional net. The spherical Ni(OH)2 particle is full of pores, crannies between cleave planes. It is supposed that this structure is beneficial to the structural stability for the spherical particles during the charge/discharge processes and can improve the cycle life of the electrode; the pores and the crannies in spherical particles can shorten the proton diffusion distance and speed its velocity, which may result in that the local polarization is lowered. The electrochemical performances of the spherical Ni(OH)2 are improved by enhancing the conducting properties of the crystalline lattice due to its quick proton diffusion.