Two novel metal–organic coordination polymers with the formulas [Zn(btdc)(2,2′-bpy)] n (1) and {[Cd2(btdc)2(2,2′-bpy)]·DMF} n (2) have been solvothermally synthesized by the assembly of mixed ligands, H2btdc and 2,2′-bpy with Zn(NO3)2·6H2O and Cd(NO3)2·4H2O, respectively, where H2btdc=2,2′-bithiophene-5,5′-dicarboxylic acid, 2,2′-bpy=2,2′-bipyridine, and DMF= N,N′-dimethylformamide. Complex 1 is composed with one-dimensional (1D) infinite zigzag polymeric coordination chains, which are further stacked into 3D supramolecular architecture by π–π stacking interaction. Complex 2 possesses 2D layers with the thickness about 1.2nm, these layers forming a 3D network through π–π stacking interactions. In complex 1, the btdc ligand exists in stable trans conformation and the conformation of btdc ligand in complex 2 is of both trans and cis. Furthermore, these two complexes show enhanced fluorescent emission in comparison with H2btdc ligand.