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Polypyrrole (PPy) was successfully prepared by chemical oxidation in various anionic surfactant solvents and an interesting regulation of the molar ratio of the oxidant and the monomer was firstly discovered which was closely related to the conductivity of the PPy when the molar ratio of the anionic surfactant to the monomer was 0.3. The value of conductivity reached its maximum when the molar ratio of the oxidant and the monomer was 1.1. A series of testing results including scanning electron microscopy, elemental analysis, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Four-Point Probes Resistivity Measurement System showed that the morphology and conducting characteristic of obtained PPy were greatly influenced by the anionic surfactant. The doping level and the degree of the structural order of counterions in the polymer chains influence the conductivity of the obtained doped PPy. POLYM. ENG. SCI., 53:2465–2469, 2013. © 2013 Society of Plastics Engineers