Polypyrroles doped with two dopants were prepared by chemical polymerization in aqueous solutions of pyrrole monomer. The solutions contained dodecylbenzenesulfonic acid (DBSA) as a dopant, tetraethylammonium tetrafluoroborate (TEABF(4)) as a codopant, and ammonium persulfate (APS) as an oxidant. The PPy composites [polypyrrole-dodecylbenzenesulfonates (PPy-DBS) codoped with tetrafluoroborate (BF4-)-PPy-DBS-BF] were soluble in m-cresol, NMP, and conditionally soluble in chloroform. Cyclic voltammetry was measured to know the electrochemical property of PPy-DBS-BF. The maximum electrical conductivity of room temperature for PPy-DBS-BF is 1.18 s/cm, which is greatly higher than that of polypyrrole doped with DBS- (0.04 s/cm). The composition and structural characterization of PPy-DBS-BF were inferred from elemental analysis, nuclear magnetic resonance, and Fourier transform infrared spectroscopy. Scanning electron microscopy was performed to know the morphology of PPy-DBS-BF. The results of UV-Vis spectra and electron spin resonance measurements showed that polaron and bipolaron existed as charge carrier of soluble PPy-DBS-BF. From the temperature dependence of the electrical conductivity, it was suggested that possible conduction mechanism for soluble PPy-DBS-BF should be hopping conduction.