A series of symmetrical and nonsymmetricalN,N-disubstituted benzimidazolium salts were synthesized asN-heterocyclic carbene precursors. These salts were treated with Ag2O to afford their corresponding mononuclear Ag(I)-NHC complexes. These compounds were characterized by spectroscopy techniques and analyzed by DFT/TDDFT and docking methods. Also, the structures of2aand2ewere determined by single-crystal X-ray crystallography. These new Ag-NHC complexes were screened for their antibacterial activities against Gram-positive, Gram-negative bacteria, fungi, and nosocomial agents.