Vat dyeing is the mainstream process of cotton fabric dyeing at present, but the high toxicity of the reducing agent and the high cost of dyeing waste liquid treatment make the process no longer meet the requirements of green and sustainable development of society. The photonic crystal structure color, which is made of nanoscale colloidal microspheres arranged in an orderly manner as structural units, is expected to be a new printing and dyeing technology, that provides a new way of thinking for dyeing cotton fabrics. However, the practical applications of photonic crystal structural colors on textile fabrics are hampered by their inadequate stability, muted color saturation, and weak mechanical properties. In this study, P(St-BA-MAA) nanospheres with a hard-core-soft-shell structure were prepared by soapless emulsion polymerization, and then P(St-BA-MAA)@PGA-Fe3+ photonic composite inks were prepared by forming a dark-colored coating film on the surface of the microspheres through the complexation of gallic acid with Fe3+. It was found that the performance of the prepared P(St-BA-MAA)@PGA-Fe3+ photonic composite ink was stable, and the dark metallic-polyphenol network film enabled the formation of vibrant non-iridescent structured colors on cotton fabrics, the soft shell of the seeded microspheres also significantly improved the adhesion between the ink and the fabrics, and the structural color fastness was greatly improved compared with the PS microspheres. The preparation of this photonic composite ink is facile, low-cost, and produces a bright color, providing practical value for the development of textile products that construct structural color effects on textile substrates.