Two series of bis(1‐alkylbenzimidazole)silver(I) nitrate and bis(1‐alkyl‐5,6‐dimethylbenzimidazole)silver(I) nitrate complexes, in which the alkyl substituent is either an allyl, a 2‐methylallyl, an isopropyl or a 3‐methyloxetan‐3‐yl‐methyl chain, were synthesized and fully characterized. The eight N‐coordinated silver(I) complexes were screened for both antimicrobial activities against Gram‐negative (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Acinetobacter baumannii) and Gram‐positive (Staphylococcus aureus, Staphylococcus aureus MRSA, and Enterococcus faecalis) bacteria and antifungal activities against Candida albicans and Candida glabrata strains. Moderate minimal inhibitory concentrations (MIC) of 0.087 μmol/mL were found when the Gram‐negative and Gram‐positive bacteria were treated with the silver complexes. Nevertheless, MIC values of 0.011 μmol/mL, twice lower than for the well‐known fluconazole, against the two fungi were measured. In addition, molecular docking was carried out with the structure of Escherichia coli DNA gyrase and CYP51 from the pathogen Candida glabrata with the eight organometallic complexes, and molecular reactivity descriptors were calculated with the density functional theory‐based calculation methods.