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A series of polymer-supported N-heterocyclic carbene silver complexes were prepared using a simple procedure via click chemistry. These complexes were tested as catalysts in the synthesis of propargylamines by the one-pot three-component coupling reaction of aldehydes, amines and alkynes (A3-coupling). The reaction was preceded smoothly to afford the corresponding products in good to excellent yields at room temperature under low catalyst loading of 0.1 mol%. Furthermore, the catalysts were stable and recoverable for six runs without a significant loss in their activity.