Photoemission studies reveal the existences of metallic Rb 4 C 6 0 and Rb 5 C 6 0 surface phases on the top layer of C 6 0 single crystal. After Rb 3 C 6 0 thin film with thickness of nanometers has formed on the (111) surface layers of the C 6 0 single crystal, the excess deposition of Rb atoms do not induce the bulk-like face-centered cubic to body-centered tetragonal or body-centered cubic structure transitions at room temperature. The large size of C 6 0 molecule offers the surface vacancies for the formation of Rb 4 C 6 0 and Rb 5 C 6 0 monolayer that is further verified by Rb3d core-level photoemission measurements. Valence band photoemission results exhibit the surface phases are metallic.