Crystal and molecular structures of adducts of uranyl pivaloyltrifluoroacetonate with hexamethylphosphoramide [UO₂(PTFA)₂(HMPA)] (I) and of uranyl trifluoroacetylacetonate with trimethyl phosphate [UO₂(TFA)₂(TMP)] (II) were determined. Compound I crystallizes in the monoclinic system, space group P2₁/n; a = 16.9384(3), b = 9.1090(2), c = 20.9844(4) Å, β = 101.5337(10)°, V = 3172.34(11) ų (at 100 K); Z = 4. Compound II crystallizes in the rhombic system, space group Pbca; a = 17.8214(4), b = 7.7786(2), c = 30.9176(7) Å, V = 4285.97(18) ų (at 100 K); Z = 8. In both cases, the cis isomer in which the neutral ligand is located between the trifluoromethyl groups is realized. Compound I differing from II by the stronger branching of ligand periphery is characterized by stronger structural deformations in the crystal.