Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th4+ metal center(s) in a monodentate manner with Th S distances of 3.7-3.8 angstrom. Th(SO4)(2)(H2O)(7)center dot 2(H2O) (1; P2(1)/m, a = 7.224(1) angstrom, b = 12,151(1) angstrom, c = 7.989(1) angstrom, ss = 98.289(2)degrees) and Th-4(SO4)(7)(H2O)(7)(OH)(2)center dot H2O (2; Pnma, a = 18.139(2) angstrom, b = 11.173(1) angstrom, c = 14.391(2) A) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO4 (3; Pnma, a = 11.684(1) angstrom, b = 6.047(1) angstrom, c = 7.047(1) angstrom) is built from chains of hydroxo-bridged, 8-coordinate Th4+ centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th4+ species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).