We report the synthesis and characterization of dendritic thiophene derivatives with their unique supramolecular assembly into 2-D crystals, nanowires, and nanoparticle aggregates. The structure and size of the dendrons and dendrimers have been confirmed with various techniques, such as NMR, SEC, and MALDI-TOF-MS. The mass values were consistent with the mass observed by MALDI-TOF-MS, whereas SEC measurements also gave useful information on the hydrodynamic volume of the individual dendrimers. The interesting electrooptical properties were highlighted by very broad absorption spectra and narrower fluorescence consistent with their electrochemical behavior. The self-organization of the dendrimers on the solid substrate is dependent on the nature of the substrate, preparation methods, and the molecule-molecule and molecule-substrate interactions. Thus, 14T-1 and 30T both formed globular aggregates on mica surface, while 14T-1 also formed nanowires on graphite surface. On the other hand, the larger 30T was observed to form 2-D crystalline structures. By varying the alkyl chain length attached to 14T-1, we were also able to obtain 2-D crystals on graphite. This showed that the different symmetry of packing for 30T and 14T-1 is also dependent on several factors, such as the molecular shape, size, and the presence of noncovalent intermolecular interactions. The results demonstrated the unique ability of thiophene dendrimers to form nanostructures on surfaces.