Single crystals of the new compounds Li 6[(UO 2) 12(PO 4) 8(P 4O 13)] ( 1), Li 5[(UO 2) 13(AsO 4) 9(As 2O 7)] ( 2), Li[(UO 2) 4(AsO 4) 3] ( 3) and Li 3[(UO 2) 7(AsO 4) 5O)] ( 4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1—monoclinic, C2/ m, a=26.963(3) Å, b=7.063(1) Å, c=19.639(1) Å, β=126.890(4)°, V=2991.2(6) Å 3, Z=2, R 1=0.0357 for 3248 unique reflections with | F 0|≥4 σ F ; 2—triclinic, P 1 ¯ , a=7.1410(8) Å, b=13.959(1) Å, c=31.925(1) Å, α=82.850(2)°, β=88.691(2)°, γ=79.774(3)°, V=3107.4(4) Å 3, Z=2, R 1=0.0722 for 9161 unique reflections with | F 0|≥4 σ F ; 3—tetragonal, I 4 1/ amd, a=7.160(3) Å, c=33.775(9) Å, V=1732(1) Å 3, Z=4, R 1=0.0356 for 318 unique reflections with | F 0|≥4 σ F ; 4—tetragonal, P 4 ¯ , a=7.2160(5) Å, c=14.6540(7) Å, V=763.04(8) Å 3, Z=1, R 1=0.0423 for 1600 unique reflections with | F 0|≥4 σ F . Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO 6 and UO 7) and different types of tetrahedral T O 4 anions ( T =P or As): PO 4 and P 4O 13 in 1, AsO 4 and As 2O 7 in 2, and single AsO 4 tetrahedra in 3 and 4. In the structures of 1 and 2, UO 7 pentagonal bipyramids share edges to form (UO 5) ∞ chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single T O 4 tetrahedra into tubular units with external diameters of 11 Å in 1 and 11.5 Å in 2, and internal diameters of 4.1 Å in 1 and 4.5 Å in 2. The channels accommodate Li + cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO 5) ∞ infinite chains. Cation–cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [OU(1)O]–U(13)–[OU(2)O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li + cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks.