Using a bioinspired approach, we prepare poly(3,4-ethylenedioxypyrrole) (PEDOP) films with parahydrophobic properties, characterized by high apparent water contact angle and strong water adhesion. The films are made by electropolymerization and the influence of substitution by an alkyl chain of various length (from C4H9 to C14H29) on the 3,4-ethylenedioxy-bridge is reported. More precisely, the best properties are obtained from a length of C12H25 due to the formation of spherical nanoparticles.