Ni(OH)2 hollow spheres have been prepared by solvent displacement crystallization using a micro-injection device, and the effect of process parameters such as concentration and the relative ratio of the injection speed of the precursor solution, which is an aqueous solution of NiSO4·6H2O, to isopropyl alcohol of displacement solvent have been investigated. The crystal phases after NaOH treatment are in the β-phase for all process parameters. A higher concentration of NiSO4·6H2O aqueous solution is injected by a micro-injection device and bigger Ni(OH)2 hollow spheres with a narrower particle size distribution are formed. The crystallinity and hardness of the as-obtained powder are so poor that hydrothermal treatment of the as-obtained Ni(OH)2 at 120oC for 24 h in distilled water is performed in order to greatly improve the crystallinity. It is thought that a relative ratio of the injection speed of NiSO4·6H2O to that of isopropyl alcohol of at least more than 1 is preferable to synthesize Ni(OH)2 hollow spheres. It is confirmed that this solution- based process is very effective in synthesizing ceramic hollow spheres by simple adjustment of the process parameters such as the concentration and the injection speed.