The $N$-heterocyclic carbene (NHC)--Ag(I) complexes 3a-c were synthesized from benzimidazolium chlorides (2a-c = NHC.HCl), incorporating benzyl derivatives and a 2-methoxyethyl group (a: $^{3}$N = 2,4,6-trimethylbenzyl; b: $^{3}$N = 2,3,5,6-tetramethylbenzyl; c: $^{3}$N = pentamethylbenzyl). The compounds were characterized by spectroscopic and elemental analyses. The synthesized NHC-Ag(I) complexes (3a-c) were tested as catalysts for the catalytic three-component coupling reaction of aldehyde, alkyne, and amine to propargylamines in various solvents. All complexes were active catalysts for catalytic three-component coupling reactions with good yields under neat and mild conditions (after 4 h, yields of up to 94%).