PbS hollow nanospheres with diameters of 80-250 nm have been synthesized by a surfactant-assisted sonochemical route. The nanostructures were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), (high-resolution) transmission electron microscopy [(HR)TEM], and scanning electron microscopy (SEM) images. Structural characterization indicates that shells of the hollow spheres are composed of PbS nanoparticles with diameters of about 12 nm. The formation of the hollow nanostructure was explained by a vesicle-template mechanism, in which sonication and surfactant play important roles. Furthermore, uniform silica layers were successfully coated onto the hollow spheres via a modified Stober method to enhance their performance for promising applications.