A monoterpyridine-poly(ethylene glycol) (monotpy-PEG) and a novel monoterpyridine-PEG-functionalized iridium(III) complex were successfully synthesized and fully characterized by means of NMR, IR, and UV-vis spectroscopy, as well as gel permeation chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The functionalized monoterpyridine I iridium(III) complex was synthesized by a bridge-splitting reaction of a dimeric iridium(III) precursor complex using a chelating terpyridine ligand with a poly(ethylene glycol) tail. With this approach, a new class of light-emitting polymeric materials revealing interesting optical properties was made avaialable.