The chemisorption of the soft scorpionate Li[PhTmMe] onto silver and gold surfaces is reported. Surface enhanced Raman spectroscopy in combination with the Raman analysis of suitable structural models, namely, [Cu(kappa(3)-S,S,S-PhTmMe)(PCy3)], [Ag(kappa(3)-S,S,S-PhTmMe)(PCy3)], [Ag(kappa(2)-S,S-PhTmMe)(PEt3)], and [Au(kappa(1)-S-PhTmMe)(PCy3)], are employed to identify the manner in which this potentially tridentate ligand binds to these surfaces. On colloidal silver surface-enhanced Raman spectroscopy (SERS) spectra are consistent with PhTmMe binding in a didentate fashion to the surface, holding the aryl group in close proximity to the surface. In contrast, on gold colloid, we observe that the species prefers a monodentate coordination in which the aryl group is not in close proximity to the surface.