In situ chemical polymerization of acid fuchsin (AF) dye in the presence of Fe3+ as a complexing and oxidizing agent in the presence of two different textile fibers such as silk and rayon were carried out by varying the experimental conditions in the N2 ambiance. The synthesized polymer systems were subjected to various analytical measurements such as FT‐IR, FES, SEM, TEM, GPC, UV‐visible spectroscopy, cyclic voltammetry, and water contact angle to assess their structure‐property relation. The electrical conductivity values of the AF grafted natural fibers were measured. The rate of grafting (RG) was calculated by using the absorption and emission spectra. The SO2 stretching of AF is seen at 1230 cm−1 in the FT‐IR spectrum. The order of grafting reaction was calculated as 0.99 based on absorbance spectrum, which proved the first‐order reaction with respect to Fe3+ concentration. The binding site and binding constant values were determined. The energy of activation (Ea) for the AF grafted rayon fiber was estimated as 30.72 kJ/mole. A plausible reaction mechanism was proposed based on the obtained experimental results.