Abstract: A novel heterobimetallic coordination polymer, [Cd8Na(ntc)6(H2O)8] (1), (H3ntc=5-nitrobenzene-1,2,3-tricarboxylic acid) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. By topology analysis, the complicated architecture of 1 is simplified to be the 6-connected α-Po (pcu) net, which is built on the unprecedented heterobimetallic Cd2Na(CO2)6 MBB. Further, a 3D Cd/Na–O framework with diamond topology was obtained on condition that all the carbon atoms were neglected. In addition, the thermal stabilities and fluorescent properties were also studied. [Copyright &y& Elsevier]