The reactivity of C₆₀^2– anion, easily generated upon chemical reduction of the C₆₀ core by sodium methanethiolate, has been systematically investigated versus a great number of saturated halogenated compounds RX or X–CH₂–R′–CH₂–X (X=I or Br), while these halo-compounds are unreactive with C₆₀ itself. Various C₆₀-derivatives in the series of bis-adducts R₂C₆₀ and fused cycloadducts R′(CH₂)₂C₆₀ are thus obtained in fair to good yields, the R or R′ groups bearing functionalities such as ethylenic double bond, halogen, ketone, alcohol, or ester moieties. On the other hand a judicious utilization of the overall mechanism of the reaction between C₆₀^2– anion and well chosen different RX and R′X compounds allow to extend this methodology to the preparation of mixed adducts RR′C₆₀. Functional adducts in the series R₂C₆₀ and R′(CH₂)₂C₆₀ are new attractive building blocks in C₆₀ chemistry, and can lead to novel highly functionalized C₆₀-based molecules. Some examples of such covalent ensembles are presented, the specific physical properties of which are typical of organic materials. To cite this article: J. Cousseau et al., C. R. Chimie 9 (2006).