New materials bearing thiophene and helicene moieties were prepared by using a potential-driven on/off switch strategy on the surface of glassy carbon and indium tin oxide substrates. Specifically, a 3-([7] helicen-9-yl)-thiophene hybrid monomer was electrooxidized in acetonitrile by using cyclic voltammetry with anodic potential limits of + 1.5 or + 2.5 V, resulting in a conductive and non-conductive polymer, respectively. The electrochemical findings were supplemented by microscopy investigations, UV/Vis, fluorescence and vibrational spectroscopies, and H-1 NMR spectroscopy as well as ellipsometry measurements and computational chemistry. The electrodeposited polymers could be used for the further development of materials applicable in organic electronics, optoelectronics, and sensing technologies.