The hexavalent uranium specie, uranyl triperoxide, UO2(O-2)(3)(4-), has been shown recently to behave like high oxidation-state d(0) transition-metals, self-assembling into polyoxometalate-like clusters that contain up to 60 uranyl cations bridged by peroxide ligands. There has been much less focus on synthesis and structural characterization of salts of the monomeric UO2(O-2)(3)(4-) building block of these clusters. However, these could serve as water-soluble uranyl precursors for both clusters and materials, and also be used as simple models to study aqueous behavior by experiment and modeling. The countercation is of utmost importance to the assembly of these clusters, and Li+ has proven useful for the crystallization of many of the known cluster geometries to date. We present in this paper synthesis and structural characterization of two monomeric lithium uranyl-peroxide salts, Li-4[UO2(O-2)(3)] center dot 10H(2)O (1) and [UO2(O-2)(3)](12)[(UO2(OH)(4))Li-16(H2O)(28)](3) center dot Li-6[H2O](26) (2). They were obtained from aqueous-alcohol solutions rather than the analogous aqueous solutions from which lithium uranyl-peroxide clusters are crystallized. Rapid introduction of the alcohol gives the structure of (1) whereas slow diffusion of alcohol results in crystallization of (2). (2) is an unusual structure featuring uranyl-centered alkali clusters that are linked into ring and spherical arrangements via [UO2(O-2)(3)] anions. Furthermore, partial substitution of Rb or Cs into the synthesis results in formation of (2) with substitution of these larger alkalis into the uranyl-centered clusters. We surmise that the slow crystallization allows for direct bonding of alkali metals to the uranyl-peroxide oxygen ligands that is observed in (2), and its Rb and Cs-substituted derivatives. In contrast, the only interaction between UO2(O-2)(3)(4-) and Li+ observed in (1) is through hydrogen bonding of the lithium-bound water. These structures potentially provide some insight to understanding how alkali counterions interact with the UO2(O-2)(3)(4-) anions during the self-assembly, crystallization and even redissolution of uranyl-peroxide polyanionic clusters.