We investigate the mechanism of 3-mercapto-1-propanesulfonate (MPS) acceleration of Cu electrodeposition in the presence of Cl– through comparison with the inactive but related model compounds 1-butanesulfonate and 1-butanethiol (BuSH). In situ shell-isolated nanoparticle-enhanced Raman spectroscopy was used to evaluate these additives as a function of potential. MPS adsorbs to the Cu electrode in the presence of Cl– through the thiol functional group. Density functional theory calculations reveal that the adsorption of thiol has a depolarizing effect on the strength of the interaction between adsorbed Cl– and the electrode surface, the consequences of which are observed spectroscopically. The sulfonate moiety does not interact directly with the electrode. However, cyclic voltammetry used to assess the permeability of adsorbed MPS and BuSH adlayers indicates that the sulfonate group has a more direct role in Cu deposition beyond simple disruption of the surface layer.