Multilayers and self-assembled monolayers of on-purpose-prepared organometallic thiolates, trans-[Pd(PBu3)(2)(SCOCH3)(2)], trans-[(C6H5C C)Pd(PBu3)(2)(SCOCH3)], and trans, trans-[(CH3COS)Pd(PBu3)(2)-(C C-C6H4-C6H4-C C)(PBu3)(2)Pd(SCOCH3)] Were deposited onto gold surfaces. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure measurements allowed us to assess the anchoring of the organometallic thiols onto gold substrates; the interaction occurring at the interface; and their molecular orientation oil the surface with tilt angles of about 30 degrees-40 degrees, depending on. the investigated molecule. The molecule packing density/coverage was also assessed.