A case of Cu-based metal-organic macrocycle, 〔[Cu2(DCT)2Br2]·1.6(C3H7NO)·1.6(CH3OH) 〕(CuBr-DCT), is constructed from thiourea–groups-containing carbazole-based ligands DCT 〔2,2'-((9-butyl-9H-carbazole-3,6-diyl)bis(methanylylidene))bis(hydrazine-1-carbothioamide)〕and characterized by single-crystal X-ray diffraction and Solid-state UV-Vis absorption spectra. CuBr-DCT shows good photochemical physical properties and can be used as a heterogeneous catalyst with excellent performance for copper-catalyzed azide-alkyne cycloaddition (CuAAC). The reaction system is composed of azide, alkyne, triethylamine (electron donor) and catalyst. As a heterogeneous catalyst, metal-organic macrocycle (CuBr-DCT) is easy to separate and recycle after the reaction, and can avoid the disproportionation or oxidation reaction of Cu(I) salt in the reaction process. CuBr-DCT exhibits excellent catalytic effect on CuAAC. Under room temperature and the irradiation of household energy-saving lamps, conversion rate is up to 100%, with no other by-products.