Abstract: In hot areas, the use of colorful environment-friendly near-infrared (NIR) reflective pigments as the exterior paint of buildings and vehicles can reduce the energy consumption of air-conditioning required for refrigeration. It can not only meet the visual needs of people, but also effectively alleviate the urban island effect. Ion doping is an important means of blending pigments.A series of (Gd_0.5Mo)_x(BiV)_1−xO₄(x=0,0.1,0.2,0.3,0.4,0.5) pigments was synthesized via co-doping with Gd³⁺ and Mo⁶⁺ by solid-state calcination. The phase structure, color performance and morphology of developed powders were investigated by colorimetric spectrophotometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible-near infrared diffuse reflectance spectroscopy. The results showed that the synthesized pigment samples had a monoclinic scheelite structure with good crystallinity, and Gd³⁺ and Mo⁶⁺ were substitute for Bi³⁺ and V⁵⁺successfully. With the increase of the doping amount, the color changes from dark yellow to bright yellow. Moreover, the synthesized pigments exhibited high NIR solar reflectance at a maximum of 82.5% in the range of 700–2500 nm. The synthesized pigment samples had good thermal stability. The yellow (Gd_0.5Mo)_x(BiV)_1−xO₄ pigments can be used as a candidate material for heat-reflecting and heat-insulating.