Self-assembly of cadmium(II) salt based on 2,3',5,5'-biphenyl tetracarboxylate with or without various N-donor ligands affords a series of coordination polymers, namely {[Cd 1 . 5 (Hbptc)(H 2 O) 4 . 5 ].2H 2 O} n (1), {[Cd 2 (bptc)(2,2'-bipy) 2 ].2H 2 O} n (2), {[Cd 2 (bptc)(pyp) 2 (H 2 O) 2 ]} n (3), [Cd(H 3 bptc) 2 (bip) 2 ] n (4), and {[Cd 2 (bptc)(bpt)(H 2 O)].H 2 O} n (5), where H 4 bptc=2,3',5,5'-biphenyl tetracarboxylic acid, 2,2'-bipy=2,2'-bipyridine, pyp=3-(pyrid-2-yl)pyrazole, bip=3,5-bis(1-imidazol)pyridine, bpt=3,5-bis(4-pyridyl)-1,2,4-triazolyl. Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectra. Complex 1 shows a 2D helical layer, which is further extended to a 3D supermolecule network through inter-layer C-H...O hydrogen bonds and π...π stacking interactions. Complex 2 exhibits a (3,6)-connected (4 3 ) 2 (4 6 .6 6 .8 3 )-kgd topology. Complex 3 possesses a 2D (3,5)-connected (4.5.6)(4.5 3 .6 4 .7 2 ) net based on 1D tube-like chains. Complex 4 has a 1D polymeric ribbon containing left- and right-handed helical chains, which are further hydrogen bonded to form a 2D supermolecule layer. Complex 5 possesses a 3D (4,5,7)-connected framework. Moreover, the fluorescent properties of 1-5 in the solid state have been investigated.