Bis-NHC and mixed NHC/PR3 copper(I) complexes (NHC = N-heterocyclic carbene) were found to be efficient catalysts enabling the azide-alkyne cycloaddition reaction leading to the formation of 1,2,3-sulfonyltriazoles under Click conditions. The mechanism of this transformation was probed and decoordination of the NHC ligand (even in the NHC/PR3 mixed ligand systems) during the catalytic transformation was observed