a [2]Rotaxane consisting of a [10]cycloparaphenylene ([10]CPP]) that binds a central bisadduct fullerene (C 60 ) with two bulky fullerenes (C 60 ) hexakis-adduct stoppers, 67 separated by two long macrocyclic spacer groups (Fig. : system 3). In the last decade, πconjugated molecules, and in particular CPP-fullerene complexes have attracted great attention for their photophysical properties and potential applications. The rotaxane we studied here as the third case is characterized by a stable "bound" state, in which the CPP ring binds the fullerene, and "unbound" states in which the CPP ring lies on the spacer groups and move toward the fullerene stoppers. While remarkable differences in the charge transport/recombination properties between those "bound" and "unbound" states have been