A new 2D cadmium(II) coordination polymer {[Cd(MBD)(L)]center dot(H2O)(2)} (n) (1) (H2MBD = 5-methoxycarbonyl-benzene-1,3-dicarboxylic acid, L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized, in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during the synthesis. In the structure of complex 1, each cadmium center is octahedrally coordinated by four O atoms from three carboxylate groups and two N of distinct L ligands. A detailed structural analysis reveales that compound 1 exhibits a unique 2D binodal (3,5)-connected (4(2).6(7).8)(4(2).6) topology structure. Furthermore, the 2D layer is extended into a 3D network through pi-pi stacking interactions. The solid-state fluorescence properties of 1 are investigated at room temperature.