A series of polyphenylene-dendronized perylenes have been synthesized, and their physical and mesoscopic properties have been investigated. The attached polyphenylene dendrons have significant effects on the physical properties of the perylenes. They increase the solubility of perylenes in common organic solvents, suppress significantly the aggregation of the perylene core, and lead to red-shifted absorption and emission. The polyphenylene dendrons give rise to a strong absorption band in the UV region and exhibit efficient intramolecular energy transfer to the perylene moiety. The functionalization of perylenes with polyphenylene dendrons allows the preparation of films by spin-coating.