A new class of ligands, N,N’-dialkyl-2,6-pyridinediamide (DRPDA), has been designed with the specific intention of exhibiting interchangeable diversity in coordination modes, including organometallic interactions, for the purpose of solvent extraction of elements relevant to the proper treatment of high-level radioactive liquid waste (HLLW) generated after nuclear fuel reprocessing. Consequently, DRPDA has been observed to extract Pd(II) and Zr(IV) from HNO3(aq) to 1-octanol in nearly quantitative yields when the selected ligand is sufficiently hydrophobic. However, concomitance of some of other HLLW components were also found. The extraction selectivity towards Pd(II) and Zr(IV) was markedly enhanced by employing ndodecane instead of 1-octanol as evidenced by good distribution ratios (DM) of Pd(II) (DPd = 72.5) and Zr(IV) (DZr = 12.9), which is several orders of magnitude greater than DM’s of other HLLW components (10−3-10−2), where addition of 20 vol% 1-octanol is still required to accelerate the extraction kinetics. Despite direct contact with the highly acidic aqueous phase, deprotonation from one of the amide NH moieties of DRPDA proceeds to form [Pd(DRPDA−)(NO3)] as a good extractables in the current biphasic system. This Pd(II) complex with a rather unique asymmetric N−^N^O tridentate coordination was characterized by SCXRD, elemental analysis and 1H NMR, and theoretically corroborated by DFT calculations and NBO analysis. In contrast, DRPDA also interacts with Zr4+ in different tridentate O^N^O mode without any deprotonation. Based on mechanistic differences in the extraction chemistry we clarified, Pd(II) and Zr(IV) co-extracted to the organic phase were recovered stepwise by using appropriate stripping agents such as 1.0 M HCl(aq) and 0.10 M HNO3(aq), respectively.