The particle size parameter is a key factor that affects radiative properties of nanopigments, and consequently, pigments of the same type but different sizes represent different spectral performance. Therefore, current study dealt with a systematic experimental investigation on the effect of TiO2 pigmented coatings on spectral reflectance and color performance of white and colored polyester fabrics in UV, VIS, and NIR region of electromagnetic spectrum, with a special emphasis on VIS region. In order to accomplish this target, polyester fabrics were coated with TiO2 nanopigment with various concentrations and different diameters, and their reflectance spectra were measured using spectrophotometric method. Two‐way analysis of variance (ANOVA) was utilized to investigate the significance of the effect of TiO2 nanopigment on the color performance of coated fabrics. According to experimental observations, an organized color shift appears in color coordinate of fabrics coated with TiO2 nanopigment of various sizes. Moreover, although TiO2 nanopigment with 35 nm diameter has the most significant impact on short wavelength region (UV region), the effect of pigment with 250 nm diameter is more noticeable on NIR region as long wavelength region.