N-heterocyclic carbene (NHCs) silver complexes are getting tremendous attention for appealing biological potentials. The present study is planned to synthesize silver-NHC complexes to investigate their anticancer potential against breast, colon and ovarian cancer cell lines. The synthesized benzimidazolium salts (C1-C2) and their binuclear silver complexes (C3-C4) were assured through spectroscopy (UV–visible, FTIR, NMR and FLR), HPLC-DAD (high performance liquid chromatography), elemental analysis as well as mass spectrometry. Molecular docking studies indicated that compound C4 has lower binding energy values of −4.49, −1.95 and −2.95 kcal/mol for Bruton’s tyrosine kinase, Human topoisomerase II alpha and Aromatase cytochrome P450 protein targets respectively. The In Vitro cytotoxicity assay confirmed the C4 is better cytotoxic agent from other studied compounds of present study having lower IC50 values of 0.996 ± 0.04, 0.97 5 ± 0.04, 0.872 ± 0.05 and 0.987 ± 0.05 µg/mL against MCF-7, A-549, A-2780 and HCT-116 cell lines. Stability of compounds in solution form studied through spectroscopy and all compounds were found stable for studied course of time. Interactions of C3-C4 with surfactants (SDS, tween-20, tween-80) have confirmed the substantial interaction to improve aqueous solubility. Interaction of C3-C4 with surfactants indicates that there is potential affinity among test compounds and surfactants for complex formation spontaneously, having strongest binding affinity for SDS (sodium dodecyl sulfate) as compared to Tween-20 and Tween-80.