Isolating isomorphic compounds of tetravalent actinides (i.e., Th-IV, U-IV, Np-IV, and Pu-IV) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and HO and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [(M6O4)-O-IV(OH)(4)](12+) building block. Prior studies have shown the predominance and coexistence of smaller species for Th-IV (monomers, dimers, and hexamers) and larger species for U-IV, Np-IV, and Pu-IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th-IV (and Zr-IV) in its isolated solid-phase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U-2) formulated as U-2(OH)(2)(SO4)(3)(H2O)(4) and a monomer-linked hexamer framework (U-U-6) as (U(H2O)(3.5))(2)U6O4(OH)(4)(SO4)(10)(H2O)(9). These structures are similar to those previously described for Th-IV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer-hexamer phases for both Th-IV, (prior) and U-IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U-2 and U-U-6 crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV-vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, ,and increased complexity, with increasing pH. This study describes a bridge across the first half the actinide series, highlighting U R similarities to TIP, in addition to the previously known similarities to the transuranic elements.