Photochemical addition of 3-diethylamino-1-propyne (DEAP) to C-60 leads to a novel fullerene adduct (1). The addition of DEAF to C-60 did not occur in the expected [2+2] fashion. Instead, addition took place at the methylene carbons alpha to the nitrogen, resulting in the replacement of two C-H bonds with C-60-C bonds. This reaction provides a facile route to a fullerene adduct containing an alkyne moiety. Study of the mechanism of addition disclosed the unexpected involvement of singlet oxygen. Other previously reported additions of amines to fullerenes also appear to involve singlet oxygen.