2-Pyrrolecarbaldiminato–Cu(II) complexes were established as efficient catalysts for the three-component 1,3-dipolar cycloaddition reaction of benzyl halides and sodium azide with terminal alkynes in water at room temperature, and several regioselective 1,4-disubstituted 1,2,3-triazoles have been synthesized under the reaction conditions in 55–97% yields.