Two new potassium uranyl phosphates, K2(UO2)2(HPO4)3·2H2O and K4(UO2)6(H2O)2(PO4)2(HPO4)5·3H2O were synthesized under mild hydrothermal conditions. K2(UO2)2(HPO4)3·2H2O crystallizes in the orthorhombic space group Pbca with lattice parameters a = 20.5125(5) Å, b = 15.0951(4) Å, and c = 11.0103(3) Å and K4(UO2)6(H2O)2(PO4)2(HPO4)5·3H2O crystallizes in the orthorhombic space group Pbcm with lattice parameters a = 10.9228(4) Å, b = 26.8147(10) Å, and c = 13.5379(5) Å. Both form in new structure types with the prior having a layered structure and the latter a framework structure. Both compounds exhibit intense fluorescence typical of uranyl compounds. Thermal analysis of each compound indicated two weight loss events up to 700 °C, one associated with dehydration of the structure and one that is likely the result of condensation of the HPO4 units. Exfoliation of the layers in K2(UO2)2(HPO4)3·2H2O is achieved using TMAH as an exfoliating agent.