Synthetic routes to aluminium ethyl complexes supported by chiral tetradentate phenoxyamine (salan-type) ligands [Al(OC(6)H(2)(R-6-R-4)CH(2))(2){CH(3)N(C(6)H(10))NCH(3)}-C(2)H(5)] (4, 7: R=H; 5, 8: R=Cl; 6, 9: R=CH(3)) are reported. Enantiomerically pure salan ligands 1-3 with (R,R) configurations at their cyclohexane rings afforded the complexes 4, 5, and 6 as mixtures of two diastereoisomers (a and b). Each diastereoisomer a was, as determined by X-ray analysis, monomeric with a five-coordinated aluminium central core in the solid state, adopting a cis-(O,O) and cis-(Me,Me) ligand geometry. From the results of variable-temperature (VT) (1)H NMR in the temperature range of 220-335 K, (1)H-(1)H NOESY at 220 K, and diffusion-ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five-coordinated aluminium central core. The geometry is intermediate between square pyramidal with a cis-(O,O), trans-(Me,Me) ligand disposition and trigonal bipyramidal with a trans-(O,O) and trans-(Me,Me) disposition. A slow exchange between these two geometries at 220 K was indicated by (1)H-(1)H NOESY NMR. In the presence of propan-2-ol as an initiator, enantiomerically pure (R,R) complexes 4-6 and their racemic mixtures 7-9 were efficient catalysts in the ring-opening polymerization of lactide (LA). Polylactide materials ranging from isotactically biased (P(m) up to 0.66) to medium heterotactic (P(r) up to 0.73) were obtained from rac-lactide, and syndiotactically biased polylactide (P(r) up to 0.70) from meso-lactide. Kinetic studies revealed that the polymerization of (S,S)-LA in the presence of 4/propan-2-ol had a much higher polymerization rate than (R,R)-LA polymerization (k(SS)/k(RR)=10.1).