The reaction of 2-(1H-pyrrol-1-yl)ethanol with 3-hydroxyflavone in the presence of copper(II) bromide yielded a dimeric copper(II) complex, [μ-O-(κ2-O,O-flav)(κ2-N,O-2PEO)Cu]2 (1) (flav = 3-hydroxyflavonolate; 2PEO = 2-(1H-pyrrol-1-yl)ethanolate) with both the flav and 2PEO ligands bound to the copper(II) atom in a κ2-bonding mode. The dimer is held electrostatically by bridging oxygen atoms between two copper atoms. Complex 1 was characterized by single-crystal X-ray diffraction, infrared, and UV-Vis spectroscopy, elemental analysis, and melting point determination. The complex crystallizes in the monoclinic space group P21/n (14) with cell values of a = 11.85340(10) Å, b = 8.51480(10) Å, c = 23.8453(2) Å; β = 99.3920(10)°.