<p>In this study, composite red pigments based on TiO₂/Fe₂O₃ were synthesized via spray pyrolysis by dispersing nanoscale TiO₂ into a Fe₂O₃ matrix. The effect of the Ti precursor on the phase formation and optical properties was systematically investigated. When titanium isopropoxide (TTIP) was used, Fe₂TiO₅ was formed, leading to a shift in hue toward orange and a loss of red coloration. In contrast, the use of colloidal TiO₂ as the precursor enabled the fabrication of vivid red composite pigments in which anatase TiO₂ and α-Fe₂O₃ phases coexisted within individual particles. The sintering temperature had a significant impact on the phase composition and optical performance of the pigments. Up to 600&#xa0;°C, the composite retained the anatase TiO₂ and α-Fe₂O₃ phases; however, at temperatures above 700&#xa0;°C, the anatase phase disappeared and Fe₂TiO₅ formed, resulting in a drastic decrease in near-infrared (NIR) reflectance. Therefore, 600&#xa0;°C was identified as the optimal sintering temperature for achieving the highest NIR reflectance while maintaining a vivid red hue. Furthermore, by increasing the TiO₂-to-Fe₂O₃ weight ratio up to 3, the chroma (C*) of the pigment steadily increased without significant changes in hue angle (24–25°), leading to a more saturated red color. At the same time, NIR reflectance improved by approximately 12% compared to pure Fe₂O₃. Temperature-rise experiments under NIR irradiation confirmed that the TiO₂/Fe₂O₃ pigments exhibited superior heat shielding performance. These results demonstrate that spray pyrolysis using colloidal TiO₂ is a simple yet effective strategy for enhancing the NIR reflectance of red pigments while preserving their desirable color characteristics. The developed TiO₂/Fe₂O₃ composites show great potential as novel cool pigments for urban heat island (UHI) mitigation applications. </p>