Eleven coordination polymers constructed from three structurally related flexible bis(benzimidazole) ligands, 1,1′‐(1,4‐butanediyl)bis(2‐methylbenzimidazole) (L1), 1,1′‐(1,4‐butanediyl)bis(2‐ethylbenzimidazole) (L2), and 1,1′‐(1,4‐butanediyl)bis(2‐benzylbenzimidazole) (L3), have been synthesized: [Zn(cin)2(L1)]·H2O (1), [Zn(cin)2(L2)] (2), [Cd(cin)2(L1)]·H2O (3), [Cd(cin)2(L2)] (4), [Ag(MES)(L1)0.5] (5), [Ag(MES)(L2)0.5]·H2O (6), [Zn(adi)(L1)]·H2O (7), [Zn(adi)(L2)0.5] (8), [Cd(adi)(L1)]·2H2O (9), [Cd(adi)(L2)] (10), and [Cd(adi)(L3)]·2H2O (11), where cin = cinnamate anion, MES = 2‐(N‐morpholino)ethanesulfonate anion, and adi = adipate dianion. For compounds 1–4, the cin anions are coordinated to metal ions in monodentate mode or bidentate chelating mode, and metal cations are bridged by L1 or L2 ligands to form 1‐D chain structures. Compound 5 shows a 1‐D chain structure which comprises a dimeric unit that is built from two silver ions and two MES anions. In compound 6, silver ions are bridged by MES anions and L2 ligands to form a 2‐D (6, 3) network while compounds 7–9 possess 2D (4, 4) networks. In the structure of compound 8, there exists a dimeric unit which is built from two zinc ions bridged by four carboxylate groups. Compound 10 exhibits a fourfold interpenetrating diamondoid net, and compound 11 displays a noninterpenetrating diamondoid framework. The luminescent properties for 1–11 are also discussed in detail.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)