Catalysis of silver nanoparticles, among the metal-based nanoparticles, has been of great interest in organic synthesis and has expanded rapidly in the past ten years because of nanosilver catalysts' unique reactivity and selectivity, stability, as well as recyclability in catalytic reactions. As can be seen from the research results reported in this critical review, the application of heterogeneous silver-based nanoparticles to general organic reactions has been proven to be an effective strategy in the development of highly efficient organic transformations in terms of efficiency and selectivity. In particular, this review revealed the strong potential of nanosilver catalysis in the total synthesis of natural products and pharmaceutical molecules.