Abstract: Zinc hydroxystannate and zinc hydroxystannate coated nano-sized calcium carbonate were synthesized as precursors by homogeneous precipitation method.Then zinc stannate coated nano-sized calcium carbonate was obtained by calcining the precursors with ultrasonic and azeotropic techniques.The calcined products of zinc hydroxystannate and zinc hydroxystannate coated nano-sized calcium carbonate were characterized by XRD and TG/DTA.Optimum condition of calcining for preparation of zinc stannate and zinc stannate coated nano-sized calcium carbonate was under 500 ℃ for 3 h.XPS results showed that zinc stannate had been coated on nano-sized calcium carbonate surface.And TEM results showed that the size of zinc stannate coated nano-sized calcium carbonate was about 40~60 nm.