CaCO3 hollow spheres were prepared easily in anion surfactants (sodium dodecylbenzenesulfonate (SDBS)) and aspartic (Asp) acid binary-additive system by using an easy rapid agitation method. The as-prepared products were characterized with scanning electron microscopy (SEM), FT-IR and X-ray diffraction. The results suggested that the CaCO3 hollow spheres have diameters ranging from 1 to 2 μm, and their wall is constituted of many nano-particles. Moreover, the possible formation mechanism of the hollow spherical structure was proposed. CaCO3 hollow spheres were prepared easily in anionic surfactants (sodium dodecylbenzenesulfonate (SDBS)) and aspartic (Asp) acid binary-additive system by using an easy rapid agitation method. The as-prepared products were characterized with scanning electron microscopy (SEM) The results suggest that the CaCO3 hollow spheres have diameters ranging from 1 to 2 μm, and their walls are constituted of many nano-particles. Moreover, the possible formation mechanism of the hollow spherical structure was proposed.