Oxidative chemical polymerization of aniline was carried out using peroxydisulphate and peroxomonosulphate as a lone initiator in an aqueous acidic medium in the presence of Rayon fiber. The Rayon fiber was tested for the chemical grafting of polyaniline onto it. The content of polyaniline (wt %) in the backbone was found to vary while varying the [M], [I], and (amount of Rayon fiber) during the polymerization of aniline. Various graft parameters like rate of grafting, % grafting, and % efficiency were calculated. Rate of homopolymerization was also followed for both cases. The chemical grafting was confirmed using FTIR spectroscopy, cyclic voltammetry, weight loss study, and conductivity measurements. Probable mechanism has been proposed to explain the experimental results obtained.