Electropolymerization of water-insoluble monomers, such as 3,4-ethylenedioxythiophene (EDOT), 3,4-dimethylthiophene (3,4-DiMeTh), 3-methylthiophene (3-MeTh), and 3-ethylthiophene (3-EtTh), proceeded successfully in aqueous electrolytes using acoustic emulsification. Ultrasonication to the water-insoluble monomer/aqueous electrolyte mixtures allowed the formation of very stable emulsions having the characteristic of giving narrow monomer droplet size distributions in the submicrometer range in aqueous electrolytes without added surfactants, and the smooth electropolymerization in the emulsions took place via direct electron transfer between the electrode and the water-insoluble monomer droplets. In this kind of electron-transfer system, the supporting electrolyte should be dissolved not only in the aqueous phase but also in the monomer droplets and contribute to the formation of an electric bilayer inside the droplets. The properties of a polymer EDOT film obtained by the present method were also investigated.