Here, we report our recent progresses in the synthesis and the study of fullerene-containing supramolecular photoactive devices. Our approach is based on the self-assembly of C₆₀ derivatives bearing an ammonium unit with functionalized crown ethers. The ammonium–crown ether interaction itself is weak and the K_a values are rather low when the association results only from the binding of the cationic unit with the macrocyclic component. However, when additional recognition elements are present, the stability of the complexes can be dramatically increased. This principle is illustrated with various examples of systems resulting from the self-assembly of C₆₀-ammonium derivatives and crown ethers bearing a porphyrin or an oligophenylenevinylene chromophore. To cite this article: J.-F. Nierengarten et al., C. R. Chimie 9 (2006).