Abstract: | A pair of novel azide‐bridged polynuclear copper(II) complexes, [CuL(μ1,1‐N3)]n ( 1 ) and [Cu4L2(CH3COO)2(μ1,1‐N3)4] ( 2 ) (L = 4‐chloro‐2‐[(2‐dimethylaminoethylimino)methyl]phenolate), have been obtained from the same Schiff base ligand and an identical synthetic procedure using anions of the metal salts as the only independent variable. Complex 1 was synthesized using copper(II) nitrate, while complex 2 was synthesized using the copper(II) acetate as the salt. Both of the complexes show novel supramolecular structures in their crystals as elucidated by X‐ray analyses. The polynuclear complex 1 contains [CuL(μ1,1‐N3)]n units as the building blocks, crystallizes in the Pbca space group. The tetra‐nuclear complex 2 contains [Cu4L2(CH3COO)2(μ1,1‐N3)4] units as the building blocks, crystallizes in the space group. |