The past decades have witnessed great advances in the synthesis, structure determination, and properties investigation of coinage metal nanoclusters. These monodisperse clusters have well-defined molecular structures, which is advantageous in correlating structures and properties. Metal nanoclusters are large molecules consisting of many components, so it is a big challenge to prepare them in a rational way. Strenuous efforts have been made to control their geometric and electronic structures, in order to optimize their various properties. A metal nanocluster normally contains a metal core and a peripheral ligand shell. The ligands do not only function as simple stabilizing agents. It has been revealed that these ligands are able to influence the formation processes of the nanoclusters, and they may also dictate the sizes, shapes, and properties of nanoclusters. There are mainly three types of ligands that are widely used as surface anchors on coinage metal nanoclusters: thiolates, phosphines, and halides. Recent ligand engineering has extended the scope to alkynyl ligands. As alkynyl ligands are versatile in interacting with metal atoms, interesting alkynyl-metal interfacial structures including linear, L-shaped, and V-shaped staple motifs can be generated, as well as a series of novel coinage metal nanoclusters that exhibit intriguing molecular geometries. The staple motifs do not simply resemble the surface structures of thiolate-protected nanoclusters, because the incorporation of alkynyl ligands may significantly alter diverse properties of nanoclusters. Compared with thiolate-protected gold nanoclusters, alkynyl-protected ones with identical metal cores exhibit distinctly different absorption profiles and show much improved catalytic activities for semihydrogenation of alkynes. In addition, the participation of alkynyl ligands could profoundly affect the luminescent properties of nanoclusters. These "ligand effects" are mainly attributed to the different nature of alkynyl ligands, as electronic perturbation through π-conjugated units may largely modulate the electronic structure of the whole cluster. In this Account, we describe the development of coinage metal nanoclusters protected with alkynyl ligands. We will first briefly bring up the emergence of alkynyl ligands as anchoring groups on the surfaces of nanoclusters. Then we present the direct reduction method for the synthesis of the following four categories of nanoclusters: (a) gold nanoclusters with mixed-ligand shells, (b) all alkynyl-protected gold nanoclusters, (c) heterobimetallic gold nanoclusters, and (d) silver nanoclusters. Their molecular structures are described, and their various alkynyl-metal interfacial structures are compared with thiolate-metal staples. Finally, ligand effects on the properties of the clusters, including optical absorption, luminescence, and catalysis, are discussed. The alkynyl ligands play an important role in terms of both structural and property aspects. We believe this Account will attract increasing attention to alkynyl ligands, which have shown promising potential in generating new structures and properties of coinage metal nanoclusters.