Silver-Tungsten-Oxide Frameworks: Isomerically pure forms of the unique isopolyoxotungstate system are incorporated into highly connected framework materials using Ag(I) as a linking unit. Thermal treatment of the materials leads to the formation of silver microparticles embedded in a tungsten oxide matrix. This novel synthetic approach promises to create a new class of nanostructured tungsten-silver-oxides with exciting physical properties, as well as exemplifies the potential for new frameworks based upon solution processable POM clusters.