Wool has disulphide bonds containing-hydrophobic external keratin layers, which act as a barrier for the modification through coating with hydrophilic materials. For that reason, in this work, to ensure a dense and homogenous conductive polymer coating onto the wool, the fabrics were subjected to the reduction process in the aqueous alkaline medium containing agents that can attack these disulphide bonds. Then, one of the polyaniline derivatives, poly(mtoluidine) (PMT), was coated onto wool by in situ polymerization of m-toluidine sulphate using ammonium persulfate (APS) as an oxidant. The effects of conditions, such as the composition of reduction-bath and types of dopants were investigated, on the mass increase (%) and surface resistivity of the composite. The reduction pretreatment of wool with sodium hydrosulphide significantly improved the coating density, conductivity, and colour shade of PMT on the surface, compared to an untreated one. The coating stability of PMT/wool composite was examined by rubbing test and detergent washing, through surface resistivity measurements. The changes in structural and surface properties of wool fabrics were determined with ATR-FTIR, contact angle, and optical microscopic techniques, respectively. The performance of PMT/wool composite was also examined in the electromagnetic shielding effectiveness (EMSE) measurements within 30 MHz-3 GHz.