The extraction of europium(III) nitrate from sodium nitrate with a series of tetrahexylmalonamides has been investigated. The tetrahexylmalonamides considered were N.N.N’N’-tetrahexylmalonamide (THMA), N,N,N’N’-tetra-hexyl-2-methylmalonamide (MeTHMA), and N,N,N’N’-tetrahexyl-2,2-dimethy-lmalonamide (DiMeTHMA). This series allowed for a systematic determination of the effects of alkyl substitution of the methylene carbon. Equilibrium modeling of the extraction data indicates that the malonamide/Eu ratio in the extracted complexes is 3 for all three malonamides investigated. This stoichiometry is different than that determined for isolated complexes. This can be rationalized by the formation of complexes with monodentate-bound diamide ligands in the extracts. The extraction constant for Eu decreases by seven-fold in going from THMA to MeTHMA, and a precipitous drop in the extraction constant occurs upon substitution of a second methyl group on the methylene carbon (i.e., for DiMeTHMA).