Ligand-protected metal nanoclusters as unique nanomaterials have attracted great attention. The protecting ligands that directly bind on the cluster surfaces are crucial in dictating the structures and properties of the clusters. In contrast to the extensively studied thiolates, alkynyl ligands have been found recently to be important ligands for passivating gold/silver cluster surfaces. In this Frontier article, recent advances in alkynyl-protected metal nanoclusters are overviewed, and the structures, luminescence and catalytic activities are also discussed. It is demonstrated that alkynyls are very promising ligands in the control of the structures and properties of gold/silver nanoclusters.