The reduction of the phenoxyimine moiety in three individual species—namely free ligand, aluminum complex, and titanium complex—with aluminum alkyls and aluminum hydride has been studied by means of DFT. It was demonstrated that the free phenoxyimine ligand in an equimolar mixture with trimethylaluminum does not undergo reduction. Instead, experimentally observed formation of the six-membered cyclic aluminum–phenoxyimine complex, useful in the ring-opening polymerization of lactones, takes place as the kinetically and thermodynamically favored process. However, it is anticipated that a 2-fold excess of the aluminum compound, especially aluminum hydride, acting on the resulting cyclic complex can convert the imine to the aluminum-subsituted amine functionality easily with an energetic barrier of approximately 10 kcal/mol. Finally, the propensity of the imine moiety in the titanium-based precursor of the coordinative olefin polymerization toward reduction with organoaluminum compounds is revealed and the mechanism of this reaction is also suggested.