Poly(styrene-methyl methacrylate-acrylic acid) photonic crystals (PCs), with five different sizes (170, 190, 210, 230 and 250 nm), were applied onto three plain fabrics, namely polyamide, polyester and cotton. The PC-coated fabrics were analyzed using scanning electronic microscopy and two UV/Vis reflectance spectrophotometric techniques (integrating sphere and scatterometry) to evaluate the PCs’ self-assembly along with the obtained spectral and colors characteristics. Results showed that surface roughness of the fabrics had a major influence on the color produced by PCs. Polyamide-coated fabrics were the only samples having an iridescent effect, producing more vivid and brilliant colors than polyester and cotton samples. It was observed that as the angle of incident light increases, a hypsochromic shift in the reflection peak occurs along with the formation of new reflection peaks. Furthermore, color behavior simulations were performed with an illuminant A light source on polyamide samples. The illuminant A simulation showed greener and yellower structural colors than those illuminated with D50. The polyester and cotton samples were analyzed using scatterometry to check for iridescence, which was unseen upon ocular inspection and then proven to be present in these samples. This work allowed a better comprehension of how structural colors and their iridescence are affected by the textile substrate morphology and fiber type.