Two entangled coordination polymers [Cd 2 (bib)(bdc) 2 ] n (1) and [Cd 2 (bib)(bda) 2 ] n (2) were synthesized by the hydrothermal reaction (bib=1,4-bis(2-methyl-imidazol-1-yl)butane, bdc=1,2-benzenedicarboxylate, bda=1,4-benzenediacetate). 1 exhibits an unusual 6-connected self-catenated 3D network based on Cd 2 (COO) 2 dimer with the point symbol of (4 4 ·6 10 ·8). 2 exhibits a 3-fold interpenetrating 3D pcu network based on Cd 2 (COO) 2 dimer. The different conformations of bib ligands (the anti–anti–anti conformation in 1 and gauche–anti–gauche conformation in 2) play the key role in the construction of different structures in 1 and 2. The luminescence and thermal stability were investigated.