A novel Cu(II) mixed-ligand complex, {[Cu(sq)(L)(H 2 O)]· 0.9H 2 O} n (1) (sq = squarate dianion, L = 5,5 -dimethyl-2,2 -bipyridine), has been synthesized and characterized by elemental analyses, infrared (IR), and X-ray single-crystal diffraction. In 1, each copper(II) ion has a five-coordinated environment with square pyramidal geometry. A one-dimensional (1D) chain structure of the complex is constructed by squarate in µ-1,2-bis(monodentate) coordination mode and further forms a two-dimensional (2D) framework via "metal chelate-metal chelate ring" π -π stacking interactions between the adjacent chains. This unexpected π -π stacking interaction provides structural evidence for the metalloaromaticity of the Cu(II)-(aromatic α,α -diimines) chelate rings.