The synthesis, adsorption behavior, surface structure, and the charge transport properties of a persulfurated coronene asterisk with a 3D-polyaromatic system, namely dodecakis(phenylthio)coronene (DPTC), deposited on HOPG(0001) and Au(111) surfaces, are investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS). DPTC molecules adsorbed on HOPG(0001) show an orbital mediated tunneling through mainly undisturbed frontier molecular states. DPTC molecules self-assemble on Au(111) into a highly ordered π-stacked columnar “edge-on pattern. The columnar stacking is a gold surface mediated process, as ascertained by fluorescence correlation spectroscopy (FCS). DPTC was monomeric in the precursor solution before assembly. The tunneling spectra of ordered DPTC stacks on Au(111) show an energetic splitting of the frontier molecular states, indicating orbital overlap and supramolecular π–π interactions of adjacent molecules. DPTCs are sufficiently flexible to facilitate dense 1D stacks. The multiple aryl-sulfur bonds play a dominant role in the modulation of the self-assembly properties of the coronenes which in turn affect their electronic properties. Our results encourage further applications in dendrimer chemistry toward molecular electronics, by using the functionalized coronene core and its multidirectional 3D properties.