Self-doped sulfonated polyaniline (PSA) has been synthesized on the surface of micellar nanoparticles made from positively charged surfactants by biocatalysis. The conformation forced by the electrostatic charge interactions between the positively charged micelle and the negatively charged PSA increases the conductivity of the PSA by three orders of magnitude. The pure PSA recovered from ion exchange, however, shows quite similar electrical properties compared with sulfonated polyanilines reported earlier. The increased conductivity of PSA complexes is as a result of the increased charge carrier concentration caused by a certain conformational locking.