To understand the binding nature of organoselenium compounds on gold, we have examined the adsorption behavior of several representative organoselenium. compounds, i.e., benzeneselenol (BSe), diphenyl diselenide, dibenzyl diselenide, dioctyl diselenide, and benzyl phenyl selenide (BPSe) on the Au surface by virtue of surface-enhanced Raman spectroscopy (SERS). BSe chemisorbs on gold as selenolate with a tilted orientation. Upon adsorption, the Se-Se bonds of diselenides are cleaved to form selenolates, analogous to the formation of thiolate monolayers from disulfides. BPSe adsorbs on gold without any C-Se bond scission. The benzyl moiety of BPSe assumes a rather vertical stance while the phenyl moiety is more tilted to the gold surface.