Three novel indole-based ligand precursors [HIndPh(R), R = methoxy, HIndPh(OMe) (); thiomethoxy, HIndPh(SMe) (); and N,N'-dimethylamino, HIndPh(NMe2) ()] have been synthesized via Sonogashira and cyclization reactions with moderate to high yield. Reactions of these ligand precursors with 0.6 equivalent of Mg(n)Bu2 in THF afforded the magnesium bis-indolyl complexes , respectively. All the ligand precursors and related magnesium complexes have been characterized by NMR spectroscopy and elemental analyses. The molecular structures are reported for compounds and . Under optimized conditions, compound demonstrates efficient catalytic activities towards the ring opening polymerization of l-lactide and ε-caprolactone in the presence of BnOH.