A biocatalytic route for the synthesis of a water soluble and conducting complex of polyaniline (PANI)/sodium dodecylsulfate (SDS) is presented. Hemoglobin is used in SDS anion surfactant. The polymerization proceeded quickly to result in a homogeneous emeraldine-colored dispersion of PANI. Absorption spectra of PANI/SDS in the aqueous dispersions at various pH values confirms that the reversibility of dedoping and redoping process of PANI/SDS and shows that the transition from emeraldine salt to emeraldine base form occurred at about pH 10.0–11.0 in this anionic micellar system. PANI/SDS in the organic solutions dedoped initially and redoped after 24 h.