Under mild hydrothermal conditions, a new organically templated uranyl zinc phosphate, [H(2)bipy](2)[(UO2)(6)-Zn-2(PO3OH)(4)(PO4)(4)]center dot H2O (UZnP-2), has been synthesized. Structural analysis reveals that UZnP-2 is constructed from UO7 pentagonal bipyramids that are linked into edge-sharing dimers that are in turn joined together by ZnO4 and PO4 tetrahedra to form a three-dimensional network. Intersecting channels occur along the a, b, and c axes. These channels house the diprotonated 4,4'-bipyridyl cations and water molecules. Ion-exchange experiments demonstrate that replacement of the 4,4'-bipyridyl cations by alkali and alkaline-earth metal cations results in a rearrangement of the framework. Further characterization of UZnP-2 is provided by Raman and fluorescence spectroscopy. The latter method reveals strong emission from the uranyl moieties with characteristic fine structure.