The control of the surface morphology is critical in the development of superhydrophobic surfaces. In this article, we report the synthesis of a novel 3,4-ethyleneoxythiathiophene (EOTT) platform and its fluorocarbon and hydrocarbon derivatives with various chain lengths (C8F17, C6F13, C4F9, C12H25, C10H21, C8H17). Their electrochemical polymerization by cyclic voltammetry is presented, as well as the characterization of the polymer films. Surprisingly, surfaces with shorter fluorinated chains presented better superhydrophobic properties with higher water static contact angles and lower hysteresis and sliding angles than the F-octyl polymer film surface. In addition, hydrocarbon analogues with long chain lengths were also superhydrophobic with stickier behavior. By increasing the hydrophobic chain length, the same variation of the surface structuration (from nanofibers to nanospheres) was observed whatever the chemical nature of the hydrophobic chain except that four additional methylene units are required for hydrocarbon derivatives.