New dinuclear copper(II) complex [Cu2(BTE)2(N3)4] (1) (BTE = 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-1,2,4-triazole)) is synthesized and characterized using single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. Single crystal X-ray diffraction reveals that complex 1 is a centrosymmetric dinuclear Cu(II) cluster unit with a Cu–Cu separation of 3.267(6) Å. In addition, complex 1 exhibits a high photocatalytic degradation activity for the degradation of rhodamine B.