By using solvated metal cations as structure-directing agents, three new iodoargentates, namely,[ Fe(DMSO) 6 ] [Ag 6 I 9 ]·DMSO (1), [Fe(H 2 O) 6 ][Ag 15 I 18 ]( 2)a nd [Cd(DMSO) 6 ] [Ag 8 I 10 ]( 3)( DMSO = dimethyl sulfoxide) have been solvothermally prepared and structurallyc haracterized. The structures of compounds 1 and 2 can be described as 1D chains constructed from the linkageo f[ Ag 6 I 9 ]a nd [Ag 5 I 11 ]b uilding units, respectively.F or compound 3,t he [Ag 10 I 22 ]b uilding blocks are directly interconnected to form a2 D[ Ag 8 I 10 ]l ayer,which are furtheri nterconnected via intermolecularf orces to generate a3 Ds upramolecular framework with 1D large channels occupied by [Cd(DMSO) 6 ] 2 + cations.I nterestingly, compounds 1-3 exhibit an ion-exchange behavior for the adsorption of as pecific dye (methylene blue, MB). Moreover, photocatalytic experimentsi ndicate that these iodoargentates can be considered as promisingp hotocatalysts for the degradation of organic dyep ollutants.[a] Dr.