We report a new tetrameric supramolecular Cu(II) complex (Cu 4 L 4 = tetrakis(N,N'-bis(salicylidene)-2,2'-ethylenedianiline)Copper(II)) with a Schiff-base ligand (H 2 L = N,N'-bis (salicylaldimine)-1,2-ethylenediamine) containing two N,O-bidentate chelate groups. Though the copper sites of Cu 4 L 4 are non-coupled, the complex exhibits a unsually high catecholase-like activity (k cat = 935 h −1 ) when the Cu 4 L 4 solution is treated with 3,5-di-tert-butylcatechol (3,5-DTBC) at basic condition in the presence of air. Combined information obtained from UV-VIS and EPR measurements could lead the suggestion of the reaction pathway in which the substrate may bind to Cu(II) ions by anti-anti didentate bridging mode.