The presence of two sulfur species was detected in X-ray photoelectron spectroscopy (XPS) studies of thiol and disulfide molecules adsorbed onto gold surfaces. These species are assigned to bound thiolate (S-2p3/2 binding energy of 162 eV) and unbound thiol/disulfide (S-2p3/2 binding energy from 163.5 to 164 eV). These assignments are consistent with XPS data obtained from different thiols (C12, C16, C18, and C22 alkane thiols, a fluorinated thiol, and a cyclic polysiloxane thiol) and different adsorption conditions (solvent type, thiol concentration, temperature, and rinsing). In particular, the use of a poor solvent for thiol adsorption solutions (e.g., ethanol for long chain alkanethiols) and the lack of a rinsing step both resulted in unbound thiol molecules present at the surface of the bound thiolate monolayer. This has implications for recent studies asserting the presence of multiple binding sites for gold-thiolate species in organic monolayers.