A simple synthetic route was developed for nonconjugated dendritic iridium(III) complex based on tunable pyridine-based ligands. From an intermediate 2-bromopyridyl-4-methanol, three series of polybenzyloxy dendritic pyridine-based ligands with 2-phenyl, 2-benzothienyl, and 2,4-difluorophenyl subsitituents were easily synthesized via two-step reactions (Suzuki reaction and etherifying reaction). Using these pyridine derivatives as the CwedgeN ligands, these dendritic iridium(III) complexes exhibiting tunable photoluminescence from blue to red were obtained. The photoluminescence quantum yields of these dendritic complexes in neat films increased with the increasing generation number of dendritic CwedgeN ligands. Importantly, these iridium complexes were used as dopants for successfully fabricating polymer-based electrophosphorescent light-emitting diodes (PLEDs) with the highest external quantum efficiency of 12.8%.