The detailed structures of most of ligand‐stabilized metal nanoclusters (NCs) remain unknown due to the absence of crystal structure data for them. In such a situation, quantum‐chemical modeling is of particular interest. We compared the performance of different theoretical methods of geometry optimization and absorption spectra calculation for silver‐thiolate complexes. We showed that the absorption spectra calculated with the ADC(2) method were consistent with the spectra obtained with CC2 method. Three DFT functionals (B3LYP, CAM‐B3LYP, and M06‐2X) failed to reproduce the CC2 absorption spectra of the silver‐thiolate complexes. The performance of different theoretical methods of geometry optimization and absorption spectra calculation for silver‐thiolate complexes was compared. It was shown that the absorption spectra calculated with the ADC(2) are consistent with the spectra obtained with CC2 method. Three DFT functionals (B3LYP, CAM‐B3LYP, and M06‐2X) failed to reproduce the CC2 absorption spectra of the silver‐thiolate complexes.