Scanning tunneling microscopy (STM) studies of monolayer of metal-free phthalocyanine (H(2)Pc) adsorbed on Au(111) have shown ordered arrangement of the molecules on the surface. Evaporation of H2Pc onto the Au(111) surface and post annealing of the sample to 670 K results in a densely packed structure of the molecules. The monolayer is characterized by molecules adsorbed with the molecular plane parallel to the substrate surface in a square adsorption unit cell. Furthermore, the high resolution images revealed the orientation of individual molecules. The H(2)Pc/Au(111) system has also been doped by rubidum and compared to the undoped layers. The Rb affects the molecular adsorption geometry, and a hexagonal unit cell is found for the coadsorption of H(2)Pc and Rb. Upon doping, highly ordered Rb-induced protrusions are observed at the benzene site of adsorbed molecules.