Abstract: This paper adopted conventional solid state reaction route to prepare a new-type inorganic pigment CaCu(3-x)ZnxTi4O12 with high near-infrared reflective properties. The structure, colour and reflective properties were investigated by XRD, Color-Eye automatic differential colorimeter and UV-vis-NIR spectrophotometer. Result showed that crystal structure changed from single phase to multi-phase with the increase of substitution degree. With the increasing of doping amount of Zn2+ ions(x=0.00-0.06), the band gap increase from 2.16eV to 2.26eV, the yellow hue b* increases from 22.35 to 29.62, and the near infrared reflectance ratio increases from 52.3% to 62.3%. The near-infrared reflectance of CaCu3Ti4O12 and CaCu2.4Zn0.6Ti4O12 pigments coating are 46.4% and 55.2% respectively. The pigments also have chemical stability and thermal stability. Therefore, the prepared CaCu(3-x)ZnxTi4O12 pigments have great application potential in “cool colorant”.