Five new transition metal coordination polymers based on H 2 tzda and co-ligand bpe, {[M(tzda)(bpe)]·H 2 O} n [M=Zn(1), Cd(2), Mn(3), Co(4)] and [Ni 2 (tzda) 2 (bpe) 2 (H 2 O)] n (5) [H 2 tzda=(1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, bpe=1,2-bis(4-pyridyl)ethane], have been hydrothermally synthesized and structurally characterized. Compounds 1–4 feature a 2D-layered architecture generated from [M(tzda)] n moiety with double-chain structure cross-linking bpe spacers. However, the conformations bpe adopts in 3 and 4 are different from those in 1 and 2 due to the rotation of C–C single bond in bpe. Polymer 5 exhibits an interesting 3D porous framework with 2-fold interpenetration, in which intriguing 1D double helix chains are observed. The photoluminescence properties of 1 and 2 in the solid-state at room temperature are investigated. In addition, variable-temperature magnetic data show weak antiferromagnetic behavior in 3–5.