The hierarchical flower-like NiMoO4 was prepared by a simple chemical precipitation in the presence of hexamethylene tetraamine, and used for electrode materials of supercapacitors. The prepared NiMoO4 shows very good electrochemical properties, such as a high specific capacity of 145.8 mAh/g at 0.5 A/g and good capacity retention. The superior properties of NiMoO4 stem from the unique hierarchical flower-like structure, which can generate more interfacial contacting between electrolyte ions and active material.