Bifunctional aminotriphenolate complexes derived from trivalent metals (M = Co, Mn, Cr) have been prepared and structurally characterized. These complexes are octahedral in the solid state but infer dynamic behavior of the ligated dimethylaminopyridine (DMAP) ligands that can function as initiators in the ring‐opening copolymerization of cyclic anhydrides and epoxides. More specifically, the ring‐opening copolymerization of cyclohexene oxide and phthalic anhydride was studied in detail, and the bifunctional Cr(III) complex gave overall the best results in terms of overall activity and polyester quality.