Cyclopropanations between C60 and readily available malonates bearing different steroid moieties (4–6) by the Bingel–Hirsch protocol has allowed the synthesis of a new series of hybrid functionalized chimeras (7–9). Whereas cycloadducts 7 and 8 showed the expected chemical structures, the presence of the diene moiety in the ergosterol unit of malonate 6 resulted in the production of the corresponding cycloadduct with an additional oxygen molecule. A thorough spectroscopical study (1H and 13C NMR, COSY, DEPT, HMQC, and HMBC) allowed the structure of monocycloadduct 9 to be unambiguously unraveled as that of an endoperoxide, as a result of the sensitizing effect of the C60 unit, which efficiently promotes the addition of excited singlet oxygen to the diene moiety of the steroid. Cyclic voltammetry of hybrids 7–9, as well as their electronic spectra, support the exclusive formation of the corresponding monoadducts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)