Polypyrrole (PPy) was prepared from different mixed-surfactant solutions with ammonium persulfate as an oxidant. Three types of combinations were selected, including cationic/anionic, cationic/nonionic, and anionic/nonionic mixed-surfactant solutions. The surfactants used in the experiments included cetyltrimethylammonium bromide (cationic surfactant), sodium dodecyl sulfate (anionic surfactant), sodium dodecyl sulfonic acid salt (anionic surfactant), poly(vinyl pyrrolidone) (nonionic surfactant), and poly(ethylene glycol) (nonionic surfactant). The morphology, structure, and conductivity of the resulting PPy were investigated in detail with scanning electron microscopy, Fourier transform infrared spectra, and the typical four-probe method, respectively. The results showed that the interaction between the different surfactants and the interaction between the surfactants and the polymer influenced the morphology, structure, and conductivity of the resulting polymer to different degrees. The cationic surfactant favored the formation of nanofibers, the addition of anionic surfactants produced agglomeration but enhanced the doping level and conductivity, and the presence of a nonionic surfactant weakened the interaction between the other surfactant and the polymer in the system. In comparison with the results for monosurfactant solutions, the polymerization of pyrrole in mixed-surfactant solutions could modulate the morphologies of PPy, which ranged from nanofibers of different lengths to nanoparticles showing various states of aggregation. (c) 2007 Wiley Periodicals, Inc.