Three new uranium arsonate compounds, UO2(C6H5)2As2O5(H2O) (UPhAs-1), UO2(HO3AsC6H4AsO3H)(H2O)·H2O (UPhAs-2), and UO2(HO3AsC6H4NH2)2·H2O (UPhAs-3) have been synthesized under mild hydrothermal conditions. UPhAs-1 is constructed from UO7 pentagonal bipyramids that are chelated by the pyroarsonate moiety, PhAs(O2)OAs(O2)Ph2–, forming chains of layered uranyl polyhedra. Two of the phenylarsonic acids are condensed in situ to form the fused tetrahedra of the pyroarsonate moiety through a metal-mediated, thermally induced condensation process. The structure of UPhAs-2 consists of UO7 pentagonal bipyramids that are chelated by phenylenediarsonate ligands, forming one-dimensional chains of uranyl polyhedra. UPhAs-3 consists of a rare UO6 tetragonally distorted octahedron (D 4h ) that is on a center of symmetry and linked to two pairs of adjacent 4-aminophenylarsonate ligands. This linear chain structure is networked through hydrogen bonds between the lattice water molecules and the −NH2 moiety. All three of these compounds fluoresce at room temperature, showing characteristic vibronically coupled charge-transfer based emission.