With a view to developing repellent materials combining both low surface energy and rough structure, original semi-fluorinated polythiophenes have been chemically and electrochemically synthesized and characterized by cyclic voltammetry, GPC, and UV-visible measurements. Polymer films have been deposited onto different substrates by drop casting a soluble polymer fraction on glass plate or by electrodeposition on ITO plate. Surface properties and particularly water and oil repellencies have been investigated by goniometry and correlated with the surface morphology and structure observed by SEM. The incorporation of fluorocarbon chains in the rigid polythiophene backbone yields very low Surface free energy materials. Moreover, the way of deposition has a huge influence on the quality and performance of the film surface properties. Electroformed polymers, due to rough surfaces, exhibit great superhydrophobic and lipophobic properties together with exceptional time stability.