The adsorption of poly(styrene) from solution on gold and copper surfaces is promoted by XPh2 substituents, where X = N, P, As, Sb. Such polymers generate ultrathin layers that were investigated with ellipsometry, contact angle measurements, X-ray photoelectron spectroscopy, infrared spectroscopy at grazing incidence reflection, and surface profilometry. The thickness of most layers is in the typical range of monolayers of flexible polymers (10-35 Angstrom), except for the polymer containing SbPh2 groups on gold, which exhibits an unusual thickness (55 Angstrom). On copper, the polymer with NPh2 groups reacts to form "thick" layers, probably consisting of organometallic complexes. In contrast to gold, copper surfaces induce the oxidation of PPh2 groups to Ph2P=O.