(Ni, Sb)-codoped rutile yellow (NiSb-RTi) pigment with a high near-infrared (Near infrared, NIR) reflectance was prepared by a solid-phase method, and then (Ni, Sb)-codoped rutile/silica aerogel (NiSb-RTi/silica aerogel) hybrid pigment with a high NIR reflectance and a network structure was prepared with SiO2 aerogel substrate. The structural characteristics, color rendering performance, NIR reflectance, and thermal insulation performance of the hybrid pigment were characterized. The results show that NiSb-RTi pigment synthesized at 1% (in mass fraction) NaF as a sintering aid has superior color rendering performance (b*=54.24) and NIR reflectance. NiSb-RTi/silica aerogel hybrid pigment with a network structure has a good color rendering performance, a low transmittance, a high NIR reflectance (i.e., 96.60%) and a low thermal conductivity (i.e., 0.068 54 W/(m·K)), indicating a superior thermal insulation performance. In addition, the preparation process and thermal insulation mechanism of the hybrid pigment with a network structure were also discussed.