Actinide partitioning is considered as one of the most challenging issues in nuclear waste remediation. Herein, we unravel a novel extraction mode pertinent to the competitive host–guest interactions for highly efficient actinide extraction. The host–guest recognition event involves binding of a room temperature ionic liquid (RTIL), 1-n-octyl-3 methylimidazolium bis(trifluoromethane)sulfonamide  (C₈mimNTf₂), as both the guest and the solvent by the hosts pillar[5]arene-based diglycolamides (P5DGAs) and the subsequent displacement of the guest by a metal ion. This two-step process suggests a unique competitive ion-mediated displacement mechanism for the metal ion partitioning in the extraction process. The supramolecular extraction system is evaluated for its extraction abilities towards actinide ions such as UO₂²⁺, PuO₂²⁺, Pu⁴⁺, Am³⁺, and fission product elements such as Eu³⁺, Sr²⁺, Cs⁺. The results demonstrate the exceedingly high distribution ratios and favorable separation of Am³⁺ and Pu⁴⁺ in nitric acid media. All the three P5DGAs form 1 : 1 complexes with Am³⁺. Time resolved laser fluorescence spectroscopic (TRLFS) studies reveal a strong complexation involving no inner-sphere water molecules in the Eu³⁺–P5DGA complexes when C₈mimNTf₂ is used as the diluent. With high efficiency in the extraction of actinides and a quantitative back extraction outcome, the RTIL-based solvent systems containing pillar[5] arene-DGA ligands developed in this work hold potential as promising candidates for nuclear waste remediation in a more sustainable fashion.