Polypyrrole (PPy) was polymerized with pyrrole (Py) as the monomer, FeCl3 as an oxidant and sodium dodecyl benzene sulfonate (SDBS) as the dopant on the surface of viscose fiber (VCF) to prepare the conductive PPy/VCF composites. Fourier transform infrared spectra (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscope (XPS) proved that the interaction between PPy and VCF formed in the PPy/VCF composites. Three structures of N atoms (imine, amine and cationic atoms) were found in PPy of PPy/VCF composites. The influence of reaction conditions including reaction time, Py concentration, FeCl3 concentration and SDBS concentration on the morphology and the conductivity of PPy/VCF composites was investigated in detail. The orthogonal experiments were designed to determine the optimal reaction conditions: reaction time 5h, Py concentration 0.1 mol/L and FeCl3 concentration 0.25 mol/L. When PPy/VCF composite was washed 50 times in water, the conductivity still kept at 1.5S/cm, and this value was stable for more washing.