Straight chain amide N,N-dihexyloctanamide (DHOA) has been found to be a promising alternative extractant to tri-n-butyl phosphate (TBP) for the reprocessing of irradiated uranium- and thorium-based fuels. Unlike TBP, DHOA displays preferential extraction of Pu(IV) over U(VI) at higher acidities (≥3 M HNO₃) and poor extraction at lower acidities. Density functional theory (DFT) based calculations have been carried out on the structures and relative binding energies of U(VI) and Pu(IV) with the extractant molecules. These calculations suggest that the differential hardness of the two extractants is responsible for the preferential binding/complexation of TBP to uranyl, whereas the softer DHOA and the bulky nature of the extractant lead to stronger binding/complexation of DHOA to Pu(IV). In conjunction with quantum chemical calculations, small angle neutron scattering (SANS) measurements have also been performed for understanding the stoichiometry of the complex formed that leads to relatively lower extraction of Th(IV) (a model for Pu(IV)) as compared to U(VI) using DHOA and TBP as the extractants. The combined experimental and theoretical studies helped us to understand the superior complexation/extraction behavior of Pu(IV) over U(VI) with DHOA.