This study investigates the formation of low-density, flat-lying decanethiol chemisorbed on Au prepared by heating the surface covered with a densely packed, upright monolayer to a surface temperature above that of the onset of desorption. We determined conditions for preparing the low-density phase by observing the evolution of the photoemission spectrum as a function of the surface temperature using polarized ultraviolet light and by utilizing scanning tunneling microscopy. The preparation conditions were similar for single- and polycrystalline gold surfaces. Once the low-density decanethiol phase was formed, reflection absorption infrared spectroscopy was employed to determine the orientation of the carbon chain backbone with respect to the Au surface. The nature of the valance electronic structure for flat-lying decanethiol is described.