Chiral polyesters, end-capped with terpyridine, were prepared via the coordinative ring-opening polymerization of L-lactide, Stable supramolecular dimer structures resulted after complexation with iron(II) ions. The formation of both the macroligands and the polymer complexes was proven for the first time clearly by means of OPC coupled to an in-line photodiode array UV/Vis spectrophotometer, NMR spectroscopy and MALDI-TOF mass spectrometry. A sensitivity of the iron(II)-centered poly(L-lactide)s towards UV irradiation and thermal or pH changes could be observed.