The surface wettability, such as superhydrophobic properties, of nanofibrous structures is highly depending on their size, length, spacing or orientation to the surface. Finding a way to control all these characteristics is extremely important in a theoretical point of view and for various applications. Here, we report the possible tuning of all these characteristics by adjusting the length (n) of the alkyl chains of electrodeposited poly(3,3-dialkyl-3,4-propylenedioxythiophene), which allows the formation of horizontally or vertically oriented nanofibers of various dimensions and spacings. Here, we play especially on the hydrophilic/hydrophobic characteristics of the polymer to change the growth of a polymer on a substrate and the distance between the polymer backbones. For example, a change in the fiber orientation from horizontal to vertical is observed for n = 2. For n < 2, the polymer fibers are mainly horizontally aligned while for n > 2, the polymer fibers are vertically aligned.