Hierarchical structures of nickel sulfide have been grown by the hydrothermal method. Nickel nitrate hexahydrate and thiourea were used as precursor materials to synthesize nickel sulfide. Ethylenediaminetetraacetic acid was used as a capping agent to achieve monodispersity. The different phases of nickel sulfide and its dependency on the precursor concentration were analyzed by X-ray diffractometry. Transmission electron microscopy analysis was used to confirm the phase changes and morphological behavior of the synthesized material. The morphological evolution of the hierarchical structure formation was studied systematically by scanning electron microscopy. In this study, we explore a novel method to control the synthesis of nickel sulfide hierarchical structures by varying the precursor concentration. The two mixed phases enhanced the catalytic activity in the 4-nitro phenol reduction reaction.