Abstract NMR spectroscopy studies on the complexation of La(III), Sm(III), Lu(III), Y(III) and Am(III) with N,N,N′,N′‐tetraethyldiglycolamide (TEDGA) have been performed. Initial studies concerning the stoichiometry of the complexes prove the formation of [M(TEDGA) 3 ] 3+ in D 2 O and [M(TEDGA) 1‐3 ] 3+ in CD 3 CN. Decreasing the solvent polarity translates to an increase of the complex stability as shown by complementary TRLFS studies with Cm(III). Due to delocalization of the lone electron pair of the amide nitrogen atom, the M(III)−O interaction has been studied indirectly by collecting 13 C and 15 N NMR data. The observed chemical shifts prove that the interaction of the trivalent ions, An(III) and Ln(III), and TEDGA is almost identical.