Two UO₂²⁺ complexes {[C₅H₄N(O)C=N-N=C(Ph)-(Ph)C=N-N=C(O)-C₅H₄N]₂UO₂(CH₃OH)} (I) and {[C₅H₄N(O)C=N-N=C(Ph)-(Ph)C=N-N=C(O)-C₅H₄N]₂UO₂(C₅H₄N(O)C=N-NH₂)} (II) were synthesized and characterized by IR, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex I belongs to monoclinic system, space group P2₁/n with a = 11.7678(4), b = 16.9667(6), c = 14.3051(5) Å, b = 98.918(3)°, Z = 4, V = 2821.64(17) ų, D_c = 1.837 Mg·m^–3, m(MoKα) = 5.805 mm^–1, F(000) = 1504, R = 0.0346 and wR = 0.0688. The crystal of complex II is of triclinic system, space group P with a = 11.6417(5), b = 11.7297(5), c = 14.2197(5) Å, α = 71.697(4)°, b = 86.020(3)°, γ = 71.572(4)°, Z = 2, V = 1748.02(12) ų, D_c = 1.742 Mg·m^–3, m(MoKα) = 4.704 mm^–1, F(000) = 894, R = 0.0283 and wR = 0.0537. The U1 is a seven-coordinate pentagonal bipyramidal configuration in I and an eight-coordinate hexagonal dipyramidal configuration in II. The thermal stability and quantum chemical calculations of I and II were also investigated.