A new solution‐processable bipolar dendrimer with carbazole units as hole‐transporting units and oxadiazole units as electron‐transporting units was efficiently synthesized based on a convergent approach by alternation of a Cu‐catalyzed azide/alkyne cycloaddition reaction and Williamson ether synthesis. The orthogonal chemistry completely avoided protection and activation of the focal points in the process of dendrimer synthesis. The dendrimer showed a wide bandgap and good thermal stability. Electrophosphorescent devices with the configuration ITO/PEDOT:PSS/bipolar dendrimer:Ir(ppy)3/TPBI/LiF/Al were fabricated. The devices showed a maximum current efficiency of 16.8 cd · A−1, a maximum power efficiency of 4.22 lm · W−1 and an external quantum efficiency of 5.7%.magnified image