Self-assembled monolayers of wE-stilbene-4-thiolate (SAM1), E-4'-(ethoxy)stilbene-4-thiolate (SAM2), and E-4'-(dimethylamino)stilbene-4-thiolate (SAM3) on Au(111) have been obtained from reaction of ethanol solutions of the corresponding S-acetyl derivatives with gold substrates. A combination of X-ray photoelectron spectroscopy, ellipsometry, and infrared reflection absorption spectroscopy indicates that the monolayers are dense (ca. 3.3 x 10(14) molecules/cm(2)) and that the long molecular axes of the thiolates are approximately perpendicular to the surface. Ultraviolet photoelectron spectroscopy shows that formation of these monolayers decreases the work function of pristine Au by 0.9-1.3 eV, in part due to a bond dipole of ca. 4.4 D/molecule formed upon adsorption and partly due to the molecular dipole moment arising from the 4'-pi-donor substituents. However, the extent of the work function variation between SAM1, 2, and 3 is smaller than anticipated from purely electrostatic considerations.