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.