Highly ordered SrMoO 4 3D spherical superstructure assembled with nanosheets was synthesized via a facile and fast sonochemical route without any template. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and selected-area electron diffraction. The results showed that the as-synthesized self-assembled SrMoO 4 spheres were composed of nanosheets with thickness of about 40−60 nm and width of 1 μm. The pH values and surfactants play an important role in the morphologies of the final sample. The possible mechanism for the formation of self-assembled SrMoO 4 spherical superstructure is proposed. The luminescence properties of these SrMoO 4 samples with different morphologies have also been investigated.