AbstractTwo cadmium(II) complexes with different dicarboxylate ligands, [Cd(ADC)(bib)0.5] (1) and [Cd(HIDC)(bib)0.5]n (2) [H2ADC = 1,3‐adamantanedicarboxylic acid, H3IDC = 4,5‐imidazoledicarboxylate and bib = 1,4‐bis(1‐imidazolyl) benzene] were obtained. Complexes 1 and 2 were characterized by single‐crystal and powder X‐ray diffraction, FT‐IR spectroscopy, and elemental analysis. The complexes showed different topological nets. Furthermore, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.