Star-shaped oligothiophenes are interesting to use in building super-structured materials. We have already used them to improve particle adhesion and assembly onto conductive substrates in an aqueous medium. In this study, electropolymerization of two different monomers, tris(2,2µ- dithienyl)methylcarbinol (TMC) and bithiophene (BT), was carried out on gold film, which was deposited by PVD on silicon wafers. The numbers of cycles and the scan rate have been changed to modify the morphology of the deposit. The polymer films were then characterised by cyclic voltammetry, classical microscopy, atomic force microscopy and scanning electronic microscopy. Polytris(2,2µ- dithienyl)methylcarbinol (PTMC) film was flatter, thicker and more uniform than polybithiophene (PBT) film. Finally electrophoretic deposition of composite particles has been carried out on PBT and PTMC films.