Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT/PSS) films with ring-, arrow-, and bubble-like micro-structures have been electrochemically generated simply by a one-step cyclic voltammetry in an aqueous media. Influences of applied potentials and surfactant/dopant-PSS on morphology of the resulting film were investigated, and a gas bubble template mechanism has been proposed. The result confirmed a well-doping of PSS in the PEDOT film. Electrochemical property and conductivity of the micro-structured PEDOT/PSS film were investigated further. Similar preparation with potential applications in fabrication of micro-devices and micro-sensors can be extended to other micro-structured conducting polymers.