Treatment of ArNHCH₂CH₂OH (HL, Ar＝2,6-Me₂C₆H₃) with AlMe₃ and ZnEt₂ resulted in the formation of a bi-aluminum complex, [(Me₂Al)(L)]₂ (1), and a tetra-zinc complex, [EtZn₂(L)₃]₂ (2), respectively. They were characterized by elemental analysis, NMR, and single-crystal X-ray diffraction analysis. Complex 1 is a crystallographically centrosymmetric dimer with an Al₂O₂ core in the solid state, while a Zn₄O₆ core is observed in 2, which can be viewed as two side-by-side cubes missing a pair of opposite vertices. Preliminary catalytic activity tests indicated that the aluminum complex 1 was inactive for the ring-opening polymerization (ROP) of ε-caprolactone, while the zinc complex 2 was a highly active initiator for the ROP of ε-caprolactone and could control the molecular weight distribution of the resulted polymers in narrow ranges.