Two new Cd(II) complexes, {[Cd(COO) 2 ] 2 Á2H 2 O} n (1) and {[CdCl(COO) 2 (Hbmi)]ÁH 2 O} n (2), were obtained through the reactions of oxalic acid (H 2 ox) with CdCl 2 Á2.5H 2 O in the presence of 1-[(benzoimidazol-yl) methyl]-1H-tetrazole (bmt) or 1-[(benzoimidazol-yl)methyl]-1H-imidazol (bmi). Single-crystal X-ray diffraction shows that complex 1 has a 3-D structure with the topological notation of (4 8 Á 62 )(4 6 Á 6 6 Á 8 3 )(4 2 Á 8 4 ), in which the oxalate displays two kinds of coordination modes: formation of the layers (μ 6 -ox) and linking the layers (μ 4 -ox). In complex 2, oxalates bridge Cd(II) ions, forming a 1-D chain, and (Hbmi) + cations coordinate to the Cd(II) ions in monodentate mode and hang at two sides of the main chain. This indicates that subtle modification of the N-donor ligands can result in complexes with different compositions and architectures. Moreover, their IR spectra, PXRD (powder X-ray diffraction) patterns, thermogravimetric analyses, and fluorescence properties are also investigated.