Aluminium and zinc complexes bearing the N,O-chelating Schiff base ligand 4,6-bis-1-(2-(dimethylamino)ethylimino)ethyl)benzene-1,3-diol, (C6H2(OH)2(NCH2CH2NMe2)2) (1a), have been synthesized. Bimetallic aluminium and zinc alkyl complexes (2a–4a) were prepared by treatment of the hexadentate 1a with the appropriate amount of AlMe3, ZnMe2 and ZnEt2, respectively. 2a has been characterized crystallographically, it lies on a crystallographic two-fold rotation axis and each aluminium centre adopts a five coordinate geometry. Complex 2a was tested as a catalyst in the ring-opening polymerisation of ɛ-caprolactone. We describe here the synthesis of two neutral ligands (1a and (C6H2(OH)2(C6H5NH2) (C=O(CH3)) (1b)) and demonstrate their application in the synthesis of molecular aluminium and zinc derivatives.