The formation of interfacial midgap states due to the reduction of buckminsterfullerene (C60) to amorphous carbon upon subsequent vapor deposition of Al is confirmed using Raman spectroscopy and X-ray, ultraviolet, and inverse photoemission spectroscopies. We demonstrate that vapor deposition of Al results in n-type doping of C60 due to an electron transfer from Al to the LUMO of C60, resulting in the formation of midgap states near the C60 Fermi level. Raman spectroscopy in ultrahigh vacuum clearly identifies the presence of the C60 anion radical (C60(•-)) as well as amorphous carbon created by further degradation of C60(•-). In contrast, the interface formed by vapor deposition of Ag shows only a slight Ag/C60 interfacial charge displacement with no evidence for complete metal-to-C60 electron transfer to form the anion radical or its further degradation products. These results confirm previous speculations of metal-induced chemical damage of C60 films after Al deposition, which is widely suspected of decreasing charge collection efficiency in OPVs, and provide key insight into charge collection at metal/organic interfaces in such devices.