Abstract: 2‐Pyrrolecarbaldiminato—Cu(II) complexes are highly efficient catalysts for the one‐pot three‐component cycloaddition of various benzyl halides with alkyl/aryl acetylenes/acetylene gas, and NaN3 leading to 1, 4‐disubstituted 1, 2, 3‐triazoles with high regioselectivity.