Silver(I)-N-heterocyclic carbene (Ag(I)-NHC) complexes of mononuclear and binuclear species, synthesised by our group and others in recent years, offer a fascinating outlook on their bioactivity. These complexes advance a range of adaptable structural patterns, leading to intra-specific variation in anticancer and antimicrobial activities. This study therefore reviews the synthesis, structural analysis and bioactivity of Ag complexes derived from mononuclear-NHC complexes either with coordinating or non-coordinating anions and binuclear NHC complexes. Specifically, the effect of stability, chain lengths and lipophilicity on the biological activity of recently reported Ag(I)-NHC complexes is reviewed. These complexes can be further explored as novel antibacterial and anticancer drugs in the nearest future.