Here, we synthesize the flowerlike bismuth molybdate (Bi2MoO6) hollow microspheres via a facile hydrothermal method. Morphology characterization suggests that this structure possesses numerous mesopores as well as high specific surface area. When we use the as-synthesized Bi2MoO6 as the supercapacitor electrode material, it shows a high specific capacitance (182 F g–1 at current densities of 1 A g–1) as well as excellent rate property (retaining 80% of the capacitance at a current density of 5 A g–1) and cyclic stability. Therefore, we can take into account the characteristics of a hollow sphere and its outstanding performance when we design and synthesis electrode materials for future energy storage systems.