We have studied decanethiolate self-assembled monolayers on the Au(001) surface. Planar and striped phases, as well as disordered regions, have formed after exposing the Au surface to a decanethiol solution. The planar phases that we observe have a hexagonal symmetry and have not been previously reported for thiols on the Au(001) surface and have lower coverage compared to that of the other known thiol planar phases such as the square α phase. The striped phases that we observe are similar to the previously reported β phase but still feature unit cells that cannot be modeled as the archetype, and the coverage is also somewhat lower. The disordered decanethiolate regions are more dynamic compared to the ordered phases, confirmed with I ( t ) spectroscopy. This suggests that in these regions the coverage is too low in order to form ordered decanethiolate phases. Our findings contribute to the growing family of possible decanethiol formations on the Au(001) surface, for which still less is known compared to the extensive overview present for the Au(111) surface.