Chemical polymerization of o-toluidine (OT) in the presence of nylon 6 and wool fibers initiated by peroxomonosulphate (PMS) in an aqueous acidic medium was carried out under nitrogen atmosphere. During the polymerization process, graft copolymers were formed along with homopolymers of OT. A procedure is given for the separation of poly(o-toluidine) (POT) grafted fiber from the homopolymer. Rate of homopolymerization (R-h), rate of grafting (R-g, percentage grafting, and percentage grafting efficiency were determined. Rate constants were evaluated from the experimental results. The chemical grafting of POT onto nylon 6 and wool fibers was confirmed through Fourier transform infrared (FTIR) spectroscopy and electrical conductivity measurements.