We performed XPS measurements to better understand the influence of the MoS2-metal surface interaction on the Mo-S binding energy. The high-resolution XPS spectra of Mo 3d and S 2p of MoS2 on different substrates are shown in Figures and, respectively. The MoS2 layer on the Au and Ag substrate exhibits a systematic broadening of the Mo 3d and S 2p peaks, which is strikingly different from previous results, where only an overall shift of Mo and S emission lines was observed. The peak fitting procedure reveal a new peak at a lower binding energy for both Mo 3d and S 2p line, which is due to the robust interaction of MoS2 with metals enabled by the UHV conditions. The lower energy lines (LEs) are more prominent on MoS2/Ag compared to MoS2/Au. The obtained S/Mo atomic ratio (shown in Supplementary Table ) reveals a higher fraction of interacting sulfur atoms in the case of MoS2 exfoliated on Ag compared to MoS2 exfoliated on Au. This can be explained by the stronger affinity of S to Ag compared to Au. This observation also agrees with the greater softening of phonon modes and explains the greater exfoliation yield obtained when using an Ag substrate compared to an Au substrate. The stronger affinity of Ag and MoS2 compared to Au and MoS2 is also evident in a first-principle study of the vdW interactions between the metal and MoS2. Nevertheless, no clear evidence of S-Au or S-Ag covalent bonding was found in the XPS spectra, which indicates that the interaction between the metal and sulfur is non-covalent. The results are shown in Figures and, respectively. On both Ag and Au metal surfaces, we obtained prominent hexagonal patterns, demonstrating the high crystalline quality of the exfoliated layers. For MoS2 on the Au substrate, we observed a pronounced broadening of the diffraction spots. At the same time, no diffraction pattern from the Au or Ag film could be observed on the produced samples, demonstrating the high polycrystallinity of the metal layers.