The adsorption of perylene on Si (0 0 1) surface has been studied by UPS measurement and DFT calculation. With 0.5 monolayer, the perylene molecule adsorbs uprightly with its long axis cross the dimer. At the coverage of 1.0 monolayer, the perylene molecule adsorbs uprightly with its short axis cross the dimer. To increase the separation between the molecules, the molecules adsorb forming a zigzag structure. With coverage increasing, the work function decreases. When the coverage is 1ML, the work function is the minimum. The dipole, formed on the surface, contributes to the change in work function. (C) 2011 Elsevier B.V. All rights reserved.