A series of zinc (Zn1–Zn6) and aluminum (Al6) complexes supported by phenoxyimine ligands (L1–L6) bearing nitrogen-containing second coordination spheres were synthesized and investigated for ring-opening polymerization (ROP) of rac-lactide (rac-LA). The ligands L1–L4 and L6 bearing sterically opened nitrogen donors resulted in dynamic NNO-chelates associated with facile nitrogen–metal coordination interactions. The bulky ligand L5 resulted in L2Zn-type complex Zn5 by disproportionation. The zinc complexes exhibited catalytic activities in ROP of cyclic monomers, including rac-LA, e-caprolactone (CL), δ-valerolactone (VL), and trimethylene carbonate (TMC). The zinc complex Zn6 bearing a bulky triphenylsilyl substituent at the 3-position of the phenoxy moiety exhibited good stereochemical control during the ROP of rac-LA to produce highly heterotactic PLAs at ambient temperature (Pr = 0.90) as well as low temperature (−30 °C, Pr = 0.94) with narrow molecular weight distributions (Mw/Mn < 1.2). The aluminum...