In recent years, self-assembled monolayers (SAMs) of selenols have been characterized using electrochemistry, scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy, and other experimental approaches. Interest in the relative stability and conductance of the Se-Au interface as compared to S-Au prompted different investigations which have led to contradictory results. From the theoretical side, on the other hand, the study of selenol-based SAMs has concentrated oil the investigation of the electron transport across the Se-Au contact, whereas the structural and the thermodynamic features of the monolayer were essentially neglected. In this Article, we examine the binding of selenols to the Au(111) surface using density functional theory with plane wave basis sets and periodic boundary conditions. Our calculations provide insights on the geometry of the headgroup, the stability of the monolayer, and the electronic properties of the bond. In particular, we propose that the presence of a conjugated backbone might be a major factor determining the relative conductance at the monolayer, by differentially enhancing the intramolecular electron transport in selenols with respect to thiols. This surmise, if confirmed, would explain the conflictive data coming from the available experiments.