Adsorbed structures of naphthalene on Cu(111) have been studied using low temperature scanning tunneling microscope (LT-STM) and low energy electron diffraction (LEED). Starting from single molecules, three kinds of long-range ordered superstructures, ( 5 3 × 5 3)R30°, (2 3 × 3)rect-1C 10 H 8 , and ( -4 1 1 -4 ) are observed depending on the molecular concentrations and the substrate temperatures during molecular adsorption.One of the self-assembled ordered phases with a (5 3 × 5 3) R30°periodicity is chiral in adsorptioninduced arrangement though a single naphthalene molecule itself has no inherent chirality. In STM images, isolated single molecules appear as depressions whereas the molecules are seen as protrusions in self-assembled layers. Coverage dependent two-photon photoemission (2PPE) spectra show that the adsorption-induced occupied states is formed at around Cu 3d bands, and this results in the enhanced tunneling of occupied state images in assembled layers.