Synchrotron-based high-resolution X-ray photoelectron spectroscopy was applied to monitor the formation of self-assembled monolayers (SAM) of alkanethiols (AT) and biphenylthiols on Au and Ag substrates. Pronounced chemical shifts in the adsorbate- and substrate-related photoemission lines upon SAM formation were observed. Only one sulfur species could be detected in the S 2p spectra of the investigated SAMs, consistent with a thiolate bond. From the fwhm's of the core level photoemission spectra conclusions on the heterogeneity of the adsorption sites and adsorption geometry can be made. The experimental data imply several (at least two) slightly different adsorption geometries for the AT moieties in AT/An. Significant final state effects in the C 1s photoemission were found for both the aliphatic and aromatic SAMs.