The interaction of uranyl(VI) nitrate with a series of bis(2-hydroxyaryl)imine (H2L1–H2L5) and bis(2-hydroxyaryl)amine (H2L8, H2L9) derivatives incorporating 1,3-dimethylenebenzene or 1,3-dimethylenecyclohexane bridges between nitrogen sites is reported. Crystalline complexes of type [UO2(H2L)(NO3)2] (where H2L is H2L1–H2L4) were isolated from methanol. X-ray structures of the complexes of H2L1, H2L2 and H2L4 show that each of these neutral ligands bind to their respective centres in a bidentate fashion in which coordination only occurs via each ligand’s hydroxy functions. Two bidentate nitrate anions complete the metal’s coordination sphere in each complex to yield hexagonal bipyramidal coordination geometries. A density functional theory (DFT) investigation of [UO2(H2L1)(NO3)2] in a simulated methanol environment is in accord with this complex maintaining its solid state conformation in solution. Solvent extraction experiments (water/chloroform) employing H2L1–H2L7 in the organic phase and uranyl(VI) nitrate in the aqueous phase showed that both amine derivatives, H2L8 and H2L9, yielded enhanced extraction of over the corresponding imine derivatives, H2L1 and H2L2. These results were further compared with those obtained for the corresponding Schiff bases incorporating 1,2-phenylene and 1,2-cyclohexane bridged ligands, H2L6 and H2L7; these more rigid systems also yielded enhanced extraction of relative to the more flexible Schiff bases H2L1–H2L5. A very significant synergistic enhancement of the extraction of by H2L1–H2L4 and H2L7 was observed in the presence of a 10-fold excess of n-octanoic acid; the influence of pH on extraction efficiency was also investigated. A parallel set of experiments employing H2L1–H2L9 as extractants for europium(III) nitrate indicated a clear uptake preference for over Eu3+ in all cases; separation of the uranyl ion from the rare earths is an important objective in mineral processing.