AbstractA new study focused on the synthesis of silver(I)‐N‐heterocyclic carbene complexes. The mono‐Ag(I)‐NHC complexes were successfully synthesized in high yield using a direct complexation method, which involved an excess of Ag2O and imidazolium salts (R= butyl, methylacetate) in dichloromethane. The bis‐Ag(I)‐NHC complexes, on the other hand, were synthesized using a 1 : 2 ratio of Ag2O and imidazolium salts. The ligands and resulting complexes were thoroughly characterized using analytical techniques such as FT‐IR, NMR spectroscopy, LC–MS and elemental analysis. Subsequently, the synthesized complexes were tested against MCF7 breast cancer cells. The results of the study highlighted the remarkable anticancer potential exhibited by the Ag(I)‐NHC complexes against breast cancer cells. Interestingly, it was observed that the mono Ag(I) NHC complexes demonstrated greater potency, with IC50 values ranging from 5 to 13.5 μg/mL, when compared to their bis‐Ag(I)‐NHC counterparts.