The radial distribution functions are calculated from large-angle X-ray scattering (LAXS) measurements for one concentrated aqueous molybdate/heptamolybdate solution and fi ve aqueous molybdophenylphosphonate solutions (lithium chloride medium). Besides water and hydrated lithium, chloride, and molybdate ions, five species in all, having different nuclearities, are postulated to exist in the solutions, according to equilibrium studies using potentiometry and P-31 NMR spectroscopy. The structures of the three polymolybdate species Mo7O246-, Mo8O264-, and (C6H5P)(2)Mo5O214-, for which the structures are determined crystallographically. are confirmed to exist also in aqueous solution. The principal structures of the remaining two complexes, (C6H5P)Mo6O21(OH2)(5)(2-) and (C6H5P)Mo7O25(OH2)(4-), are elucidated with the use of structures of related species. Bath anions have one group of four edge-sharing MoO6 octahedra and another group of two MoO6 octahedra connected by sharing corners, forming a bent unsymmetric six-membered ring, with the C6H5PO3 group placed on the crowded side of the ring. In the former,, the group of two MoO6 octahedra is edge-shared, while in the latter, the group is face-shared, resulting in a ring small enough to tetrahedrally coordinate to the seventh molybdenum opposite the phenyl group.