Reactions of MCl 2 (M=Mg, Ca, Sr, Ba) and a4-ptz (a4-ptz=5-[N-acetato (4-pyridyl)] tetrazolate) potassium salt in water, respectively, and produced four new complexes [Mg(H 2 O) 6 ]·(a4-ptz) 2 ·2H 2 O (1), [Ca(a4-ptz) 2 (H 2 O) 2 ] n ·2nH 2 O (2), [Sr(a4-ptz) 2 (H 2 O) 2 ] n ·2nH 2 O (3), [Ba 4 (a4-ptz) 8 (H 2 O) 8 ] n ·4nH 2 O (4). These compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compound 1 has mononuclear structure bearing distinct intermolecular hydrogen-bond interactions to form a three-dimensional supramolecular network. While compounds 2–4 have one-dimensional polymeric chains that are bridged by two water molecules linker, respectively. The luminescence properties of 1–4 were investigated at room temperature in the solid state.