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Silica hollow microspheres with a single hole in the shell have been prepared by a Pickering emulsion route.The CaCO3 microspheres as template were embedded partly onto paraffin wax by a Pickering emulsion method, and then SiO2 shell cover on the outside surface of CaCO3 microspheres, after removal of the wax and the CaCO3 core, single-hole hollow SiO2 microspheres were obtained.We observed that the calcinations of CaCO3 microspheres is essential for the formation of wax@CaCO3 emulsion particles, while the arrangement of the CaCO3 microspheres on the surface of the paraffin wax particles could be tuned by adjusting CaCO3-to-paraffin wax mass ratio and HCl etching.The hole size of SiO2 microspheres could be adjusted by using various concentrations of surfactant cetyltrimethyl ammonium bromide (CTAB), which effect the penetration distance of CaCO3 microsphere onto paraffin wax.The size of SiO2 microspheres were tailored by using various size of CaCO3 microspheres.By optimizing the experimental conditions, the single-hole hollow microspheres with hole sizes of 220-800 nm and particle sizes of 0.8-1.8 μm were synthesized.