A new extractant for the separation of actinide(III) and lanthanide(III), bis(o-trifluoromethylphenyl)phosphinic acid (O-PA) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(o-trifluoromethylphenyl)dithiophosphinic acid (S-PA). Multinuclear NMR spectroscopy was used for elementary characterization of the new O-PA derivative. This new O-PA extractant was used to perform Am(III)/Eu(III) separations and the results were directly compared to those obtained in identical separation experiments using S-PA, an extractant that is known to exhibit separation factors of ∼100,000 at low pH. The separations data are presented and discussed in terms comparing the nature of the oxygen atom as a donor to that of the sulfur atom in extractants that are otherwise identical.