Relativistic density functional theory has been applied to the uranyl(VI) and uranyl(V) complexes of unsubstituted (1) and dodeca-alkyl-substituted (2) isoamethyrin (hexaphyrin(1.0.1.0.0.0)). The experimentally observed bent conformation in the uranyl(VI) complex of 2 (Sessler, J. L. et al. Angew. Chem., Int. Ed. 2001, 40, 591) is reproduced accurately by the calculations. It is entirely due to the external alkyl substitutents; the unsubstituted complexes of 1 are planar. Complex geometry and stability are seen to be the result of two competing factors; aromatic stabilization favors a planar conformation of the macrocycle whereas the bending affords a much better fit between the cavity and the uranyl cation. The uranyl(VI) complex of 2 is more stable than that of 1 as a result; the trend is reversed for the larger uranyl(V) cation. An energy decomposition analysis shows that the differences between U-VI and U-V originate in the different capabilities of these cations for covalent and/or polarization interactions with the ligands rather than in sterical factors.