The design and construction of polyoxometalate (POM)-templated silver clusters have received increasing attention, not only due to their aesthetic structures but also to their wide applications in chromatic materials, magnetism, electronics, and fluorescence. Among various POM-templated silver clusters, asymmetrically-wrapped POM–silver clusters have unusual structures: POMs have exposed surfaces and an asymmetrically-connected silver shell, which endows the clusters with distinctive properties, such as redox and electrocatalytic activities. This review summarizes recent developments in this field, highlighting the syntheses, structures, and properties of the asymmetrically-wrapped POM–silver clusters. The formation mechanisms, challenges, and perspectives of such clusters are also discussed. We believe that this review will motivate the development of the asymmetrical templation effect of POM in silver clusters.