Three Ag(I) coordination polymers with flexible long-chain multi-nitrile ligands, [Ag(TDPN)(NO 3 )] n (1), [Ag(TDPN)(ClO 4 )] n (2) (TDPN=β,β′- thiodipropionitrile), [Ag 2 (TCEB)(NO 3 ) 2 ] n (3) (TCEB=1, 2, 3, 4-tetrakis (2-cyanoethoxy)butane) have been synthesized and structurally characterized by IR spectra and X-ray crystallography. In particular, TCEB is a meso compound. Single-crystal X-ray analysis shows that it contains two chiral carbon atoms with R- and S-configurations. The structures of 1, 2 and 3 consist of a 1-D ladder-like chain, a 2-D boxlike network and a 3-D framework of CdSO 4 topology, respectively. IR spectra of the free and coordinated CN groups, the correlation between the counter anions and the topological structures, and the photoluminescent properties of complexes 1–3 are also discussed.