A series of gallium and indium complexes containing a bis(imino)phenolate ligand framework were synthesized and completely characterized with different spectroscopic techniques. The molecular structures of a few complexes were determined using single crystal X-ray diffraction studies. These compounds were found to be extremely active towards the bulk ring opening polymerization (ROP) of lactides yielding polymers with high number average molecular weight (Mn) and controlled molecular weight distributions (MWDs). The neutral complexes 1–8 produce isotactic enriched poly(lactic acid) (PLA) from rac-lactide (rac-LA) under melt conditions, whereas the ionic complex 9 produces atactic PLA. The polymerizations are controlled, as evidenced by the narrow molecular distribution (MWDs) of the isolated polymers in addition to the linear nature of number average molecular weight (Mn) versus conversion plots with variations in monomer to catalyst ratios. The kinetic and mechanistic studies associated with these polymerizations have been performed.