Coinage metal-alkynyl clusters have been developed rapidly over the past few decades. An attractive area of this field is the integration of polyoxometalates (POMs) to direct the formation of metal-alkynyl clusters. POMs are metal-oxide clusters with unique structural diversity and tunable properties, and by incorporation of POM anions into the skeleton, the resulting clusters could be stabilized, functionalized, and so on. Herein, we summarize the advances in POM-based homo and heterometallic copper/silver-alkynyl clusters.