Sulfur-bearing nickel was prepared by a direct electrodeposition in an ammoniacal Ni(II) electrolyte containing thiourea. This sulfur-bearing nickel showed an excellent dissolving activity when used as anodic materials in the traditional Watt bath. The influence of thiourea on the surface microstructure, crystallization texture, and electrocrystallization process of sulfur-bearing nickel were investigated by scanning electron microscopy, X-ray diffraction, and electrochemical techniques. The results show that the S element is uniformly distributed in the electrodeposited nickel. The prepared nickel samples present a blade shape microstructure, and the blade size decreases by the addition of thiourea. Sulfur-bearing nickel exhibits face-centered cubic structure and (111) preferred orientation, and the orientation distribution is strengthened with increased thiourea concentration. The nucleation parameters, such as N (0), A, and J (0), are obtained from the initial parts of the transients making use of Sharifker-Mostany theoretical model. Both the nucleation rate and the vertical growth rate are increased by the addition of thiourea, leading to finer grains and better dissolving activity.