The system of CuI and NBS was found to provide both I (+) and Cu (+) for the first time. An efficient method for preparation of 5-iodo-1,4-disubstituted-1,2,3-triazole was achieved by multicomponent one-pot reaction of azides with alkynes in the presence of the novel CuI and NBS catalytic system. The high tolerance of various sensitive groups revealed the potential applications of this method in organic synthesis and drug discovery.