The synthesis of novel C60-donor dyads in which the fulleropyrrolidine moiety is covalently attached to an π-extended tetrathiafulvalene analogue through an ethylenic spacer is described. The cyclic voltammetry confirms the redox reactivity of both donor and acceptor chromophores and the semiempirical PM3 theoretical calculations predict the existence of two conformational isomers. In the ground state, no evidence of charge transfer interaction was observed in solution. Upon excitation, the fullerene singlet excited state in C60-donor dyads is subject to a solvent-dependent, rapid fluorescence quenching, suggesting an intramolecular electron transfer.