Individual polyphenylene dendrimer 1 and their self-assembled nanostructures, prepared by spincoating and solvent casting on various substrates such as mica, silanized mica, and highly oriented pyrolytic graphite (HOPG), have been investigated by noncontact atomic force microscopy. Besides globular clusters and monolayers, polyphenylene dendrimer 1 self-organizes into micrometer long nanofibers on a HOPG surface. Fibrillar nanostructures have also been visualized on a silanized mica surface, while on a mica surface the dendrimers only aggregate into globular clusters. Two possibilities for the development of dendrimer nanofibers are proposed.