The formation and surface structure of pentafluorobenzenethiol (PFBT) self-assembled monolayers (SAMs) on Au(111) formed under various experimental conditions were examined by means of scanning tunneling microscopy (STM). Although it is well known that PFBT molecules on metal surfaces do not form ordered SAMs, we clearly revealed for the first time that the adsorption of PFBT on Au(111) at 75 degrees C for 2 h yields long-range, well-ordered self-assembled monolayers having a (2 x 5 root 13)R30 degrees superlattice. Our results will provide new insight into controlling the structural order of PFBT SAW which will be very useful in percisely tailoring the interface properties of metal surfaces in electronic devices.