A synthetic method for 2-bromoimidazoles is developed from Rh-catalyzed cyclization of N-sulfonyl-1,2,3-triazoles with bromocyanides. Cu-catalyzed [3 + 2] cycloaddition followed by Rh-catalyzed cyclization starting from alkynes, N-sulfonylazides, and bromocyanides is also demonstrated for de novo synthesis of 2-bromoimidazoles in one pot. Moreover, this work was successfully employed to introduce diverse functional groups to the 2-position of imidazoles via cross-coupling reaction.