A series of six coordination polymers based on octahedral cluster anions Re Q (CN) (Q = S or Se) and Ag cations coordinated by bipyridine analogs were synthesized under solvothermal conditions. Their structures have been characterized by single crystal X-ray diffraction. Compounds and described by the general formula {Ag(phen)} Re Q (CN) (Q = Se ( ), S ( ); phen = 1,10-phenanthroline) exhibit layered structures assembled into a supramolecular network by CH…π contacts. At the same time, compounds {Ag(bipym)} Ag Re Se (CN) (bipym = 2,2'-bipyrimidine) ( ), {Ag (bipy)}Ag Re Se (CN) ·CH CN (bipy = 4,4'-bipyridine) ( ) and {Ag(dpbp)} Re Q (CN) ·2H O·2CH CN (Q = Se ( ), S ( ); dpbp = 4,4'-Di(4-pyridyl)biphenyl)) evince framework structures. In , , and weak Ag⋯Ag interactions are observed. All the compounds show luminescence in the red region. The luminescence quantum yields and lifetimes were found to be notably higher than those for most of the coordination polymers based on the octahedral rhenium cluster complexes.