An electro-responsively reversible switching of wettability between superhydrophobicity and superhydrophilicity has been obtained from a highly porous structured polythiophene film. The polythiophene film was prepared by two-step electrochemical deposition on an indium tin oxide (ITO) substrate. The underlying poly(3,4-ethylenedioxythiophene) (PEDOT) provides a highly porous structured conductive support, and poly(3-methylthiophene) (P(3-MTH)) deposited thereon plays the role of a low-surface-energy conductive coating. The wettability switching of this double-layer film between superhydrophobicity and superhydrophilicity has been investigated by doping and dedoping in an electrolyte solution containing ClO4–. Electrochromism of the film was also seen to accompany the electrochemical process of conversion between the two superwetting states. On the basis of this porous electro-active film, an in situ electro-wetting device was also demonstrated.