Five new coordination polymers, namely, [Zn(HL)(bib)](n)center dot 2nH(2)O (1), [Zn-2(L)(mu(3)-OH)(H2O)]n center dot 2nH(2)O (2), [Cd-1.5(L) (H2O)(2)](n)center dot 0.5nH(2)O (3), [Cd-1.5(L) (CH3CN)](n)center dot 0.5nH(2)O (4) and [Cd-1.5(L)(bib)(H2O)(2)](n)center dot nH(2)O (5), (H3L = biphenyl-2,4',5-tricarboxylic acid, bib = 4,4'-bis(imidazol-1-yl)phenyl) have been synthesized under solvothermal conditions. Complexes 15 have been characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Complex 1 shows a 2D (4,4) network and further forms a 3D supramolecular framework by pi-pi interactions. Complex 2 is a 3D framework based on infinite rod-shaped chains. Complex 3 exhibits a 3D framework with a (3,4,5)-connected {4(2).6}(2){4(2).8(4)}{4(3).6.8(6)}(2) topology. Complex 4 features a 3D network with a (4,4,6)-connected {4(4).6(2)}(3){4(6).6(7).8(2)}(2) topology. 5 displays a 3D 2-fold interpenetrating (4,4,4)-connected framework with a point symbol of {4.6(4).10}(2){4.6(4).8}(2){6(2).8(4)}. Moreover, the thermal stabilities and photoluminescence properties of 1-5 have been investigated.