Functionalization of a red phosphorescent iridium(III) complex core surrounded by rigid polyphenylene dendrons with a hole-transporting triphenylamine surface allows to prevent the intermolecular aggregation-induced emission quenching, improves charge recombination, and therefore enhances photo- and electroluminescence efficiencies of dendrimer in solid state. These multifunctional shape-persistent dendrimers provide a new pathway to design highly efficient solution processable materials for phosphorescent organic light-emitting diodes (PhOLEDs).