Poly(3,4-ethylenedioxythiophene) (PEDOT) with three-dimensional (3D) flowerlike nanostructures was fabricated by chemical oxidation polymerization in a ternary phase system, which was composed of the surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT), aqueous FeCl₃ solution and p-xylene. This kind of 3D flowerlike PEDOT formed by nanofibers was prepared by controlling the molar ratio of water (used to dissolve FeCl₃) to the surfactant, AOT. This molar ratio is defined as N which equals n_H2O/n_AOT. In particular, both the conductivity and specific surface area increased with the molar ratio, N, increasing. The room temperature conductivity of the synthesized PEDOT reached a relative high value of 137 S cm⁻¹. Moreover, the novel 3D flowerlike nanostructures endow a high specific surface area of around 46 m² g⁻¹. The measurements of UV-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS) indicate that the doping level played a key role in improving conductivity of PEDOT. This study is significant to the potential applications of PEDOT on supercapacitors, sensors, actuators, transistors, and so on.