A series indole-based ligand precursors, PzRIndH (R = H, PzHIndH; R = Me, PzMeIndH;R = t-Bu, PztBuIndH; and R = Ph, PzPhIndH), have been synthesized via copper-catalyzed N-arylation (for PzHIndH) or the Bartoli indole synthesis (for PzMeIndH, PztBuIndH and PzPhIndH) reactions with moderate to high yield. Reactions of these ligand precursors with 0.7 equivalentof MgnBu2 in THF (for 1) or hexane (for 2–4) afforded the bis-indolyl magnesium complexes 1–4,respectively. All the ligand precursors and related magnesium complexes have been characterizedby NMR spectroscopy and elemental analyses. The molecular structure is reported for compound 1.These novel magnesium complexes demonstrate efficient catalytic activities for the ring-opening polymerization of L-lactide in the presence of alcohol.