Aluminum complexes of non-chiral-salalen ligands were investigated in the catalysis of Ring-Opening Polymerization (ROP) of lactide and -caprolactone and in their copolymerization. The aluminum-salalen complexes were found to polymerize all varieties of lactide, namely: L-, D-, rac- and meso-lactide and showed moderate productivities. Rac-LA gave rise to isotactic polylactide (with Pm up to 72%), while meso-LA gave rise to heterotactic polylactide (with Pm of 79%). An experiment was designed for distinguishing between chain-end control and enantiomorphic-site control combined with polymeryl exchange for the isotactic stereoblock microstructure observed for the PLA produced from rac-LA; it gave a strong evidence for polymeryl exchange between propagating species. Finally, this class of catalysts promoted the copolymerization of ε-caprolactone and lactides. In particular, compound 2b allowed controlled random copolymerization of ε-caprolactone and L-lactide.