Various diglycolamides (DGAs), N,N,N',N'-tetraoctyl diglycolamide (TODGA), N,N-di-2-ethylhexyl-N',N'-di-octyl diglycolamide (DEHDODGA), N,N,N',N'-tetra-2-ethylhexyl diglycolamide (TEHDGA), N,N-di-decyl-N',N'-di-hexyl diglycolamide (D(2)DHDGA), N,N-di-butyl-N',N'-di-dodecyl diglycolamide (DBD(3)DGA), N,N,N',N'-tetra-hexyl diglycolamide (THDGA), and N,N,N',N'-tetradecyl diglycolamide (TDDGA) have been synthesized and studied for the extraction of Am(III) and Eu(III) from nitric acid medium. An attempt was made to understand the extraction and third phase formation behavior of trivalent metal ions in these DGAs. Our results revealed that despite having the same carbon to oxygen ratio in these DGAs, the third phase formation behavior and extractions achieved in these DGAs are significantly different.