Self-assembled monolayers (SAMs) of 1,1'-biphenyl-4-thiol (H-(C(6)H(4))(2)-SH) on Au(111) were prepared from solution or via vapor deposition in ultrahigh vacuum and characterized by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and X-ray photoelectron spectroscopy (XPS). In contrast to the typically observed for densely packed alkane-thiol SAMs on Au(111) (√3 × √3)R30° structure, the densely packed aromatic biphenylthiol SAMs prepared by both methods exhibit an unusual hexagonal (2 × 2) structure. Upon annealing at 100 °C, this structure evolves into the (2 × 7√3) structure resulting in the formation of highly ordered pinstripes oriented along the [1 -1 0] directions. Lower density SAMs, prepared by vapor deposition in vacuum, show mixed structures comprising the hexagonal (2 × 2) structure and two rectangular arrangements with the unit cells of (3√3 × 9) and (2√3 × 8). An extinction of the (3√3 × 9) structure in the favor of the (2√3 × 8) structure is observed upon annealing at temperatures of ~100 °C.