The anilido-aldimine chelating ligands (1R,2R)-[(NHAr)C6H4CH=N]2C6H10 (Ⅱ: Ar = C6H5; Ⅲ: Ar = 2,6-Me2C6H3) reacted with Al(CH3)3 to afford dinuclear aluminum complexes (Ⅳ, Ⅴ), respectively. All the complexes were characterized by 1H and 13C NMR spectroscopies. Complex Ⅴ was additionally characterized by single crystal X-ray diffraction analyses. The X-ray analysis reveals that the molecular contains two aluminum centrals and single ligand. Catalysis of the aluminum complexes Ⅳ, Ⅴ towards the ring-opening polymerization of ε-caprolactone was investigated in the presence of benzyl alcohol. All the polymerization reactions proceed in a controlled/living manner. The conversion exceeds 97% within 1.5 min using n(ε-caprolactone)∶n(BnOH)∶n(Ⅳ or Ⅴ) =200∶4∶1. Turn over frequency for Ⅳ is 7840 h–1, and for Ⅴ is 9700 h–1, much higher than the ethyl-bridged binuclear aluminum complex (1152 h-1) and the mononuclear amine-imine aluminum complex (2550 h-1). The polymerization reactions proceed in a controlled manner.