Systematic control of the reactions between U(VI) and 1,4-phenylenebis(methylene))bis(phosphonic acid) (pmbH(4)) allows for alterations in the bonding between these constituents and affords three uranyl phosphonate compounds with chiral one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) structures, namely, [TPA][UO2(pmbH(3))(pmbH(2))H2O]center dot 2H(2)O (1), [NH4](2)[UO2(pmb)] (2), UO2(pmbH(2)) (3), and the first uranyl mixed phosphite/phosphonate compound [TMA](2)[(UO2)2(pmb)(HPO3)] (4) (TPA = NPr4+, TMA = NMe4+). These compounds crystallize in the space groups P2(1)2(1)2(1), P (1) over bar, P2(1)/c, and Cmcm, respectively. Further investigation of the local uranyl coordination environment reveals that in 1 only oxygen atoms from P-O moieties ligate the uranium centers; whereas in 2 only P-O- oxygen atoms are involved in bonding and yield a layered topology. Compound 3 differs sharply from the first two in that conjugated P-O and P-O- oxygen atoms chelate the uranium centers resulting in a 3D framework. In compound 4, a phosphonate group bridges three uranyl centers further coordinated with a phosphite ligand HPO32-, which is a product of pmbH(4) decomposing, forming a 2D layered structure. Compounds 3 and 4 also contain a different coordination environment for U(VI) than that found in 1 or 2. In this case, tetragonal bipyramidal UO6 units occur instead of the far more common UO7 pentagonal bipyramids found in 1 and 2. Interestingly, 1 converts to 3 at elevated reaction temperatures, indicating that the formation of 1 is likely under kinetic control. This is supported by thermal analysis, which reveals that 3 has higher thermal stability than 1 or 2. UV-vis-near-IR absorption and fluorescence spectroscopy show that the absorption and photoluminescence intensity increases from 1 to 4. Density functional theory electronic structure calculations provide insight into the nature of the interactions between U(VI) and the phosphonate ligands.