We try to understand the fact that fullerene film behaves as n-type semiconductor in electronic devices and establish a model describing the energy level alignment at fullerene/metal interfaces. The C60/Ag(100) system was taken as a prototype and studied with photoemission measurements. The photoemission spectra revealed that the Ag atoms of the substrate diffused far into C60 film and donated electrons to the molecules. So the C60 film became n-type semiconductor with the Ag atoms acting as dopants. The C60/Ag(100) interface should be understood as two sub-interfaces on both sides of the molecular layer directly contacting with the substrate. One sub-interface is Fermi level alignment, and the other is vacuum level alignment.