In this original work, we want to control the shape of the resulting porous structures by templateless electropolymerization, by adjusting the spacer (flexible alkyl chains or rigid aromatic groups) between thieno[3,4-b]thiophene and carbazole used as the monomer and the substituent, respectively. A huge change is especially observed from ribbon-like structures to nanorings as the alkyl spacer increases. The presence of a significant amount of water is necessary for the formation of these porous structures because it allows releasing a high amount of gas bubbles. The size and number of nanorings are dependent on both the alkyl spacer and electrochemical parameters such as the number of deposition scans.