Diels–Alder reaction of endocyclic, acyclic 1,3-dienes or (hetero) o-quinodimethanes with the dienophilic fullerene C₆₀ is presented as an efficient tool for linking electroactive units giving rise to systems where both the donor and C₆₀ partners take up well defined volumes and orientations with respect to one another. While porphyrin is the most frequently used electron donor in artificial photosynthetic models, C₆₀-based tetrathiafulvalene (TTF) or π-conjugated oligomer adducts remain interesting candidates for the preparation of photovoltaic devices. In this account, we focus on the use of the Diels–Alder cycloaddition and its use in the synthesis of TTF–C₆₀ dyads, (TTF)_n–C₆₀ polyads and C₆₀–TTF–C₆₀ dumbbells as part of ongoing research into materials which display efficient photo-induced electron transfer. To cite this article: P. Hudhomme, C. R. Chimie 9 (2006).