Hollow calcium carbonate ( CaCO3 ) microspheres were prepared in aqueous solution with the presence of polyoxyethylene (20) sorbitan monolaurate (Tween20) and sodium dodecyl sulfate (SDS).The microspheres were characterized with X-ray diffraction (XRD),scanning electron microscopy (SEM) and transmission electron microscope (TEM).The X-ray diffraction data showed that the hollow CaCO3 microsphere consisted of calcite crystals.The influence of Tween20 and SDS concentrations on the morphology of CaCO3 crystals was investigated.The results suggested that the “core-shell model” of Tween20/SDS micelle aggregated as templates,which could control the growth of hollow CaCO3 microspheres.The interaction between mixed surfactants and calcium ions played a critical role in organizing calcium carbonate in microscopic level.