Three different tetrazole‐carboxylate ligands, Hpymtza, Hpytza, and H2dtzeda were chosen to be reacted with Ca(NO3)2·4H2O, resulting in the formation of three coordination compounds, [Ca(pymtza)2(H2O)4] (1), [Ca(pytza)2(H2O)2] (2), and [Ca(dtzeda)(H2O)2] (3) [Hpymtza = 5‐(2‐pyrimidyl)tetrazole‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid, and H2dtzeda = 1, 2‐bis(tetrazol‐5‐yl)ethane‐N1, N1′‐diacetic acid]. X‐ray diffraction analysis revealed that compound 1 displays a mononuclear structure, compound 2 is a one dimensional zigzag chain structure, whereas 3 shows a three‐dimensional structure. The structures were controlled by not only the different substituents of the tetrazolyl ring, but also the complementary hydrogen bonds. Furthermore, the luminescence properties of compounds 1–3 were investigated at room temperature in the solid state. These emissions can be tentatively attributed to the ligand centered emission.