The convergent synthesis of large monodisperse dendrimers, up to the fourth generation, decorated in their periphery with pi-extended tetrathiafulvalene units is reported, and their redox and supramolecular properties are investigated. A number of experiments (MALDI-TOF, H-1 NMR at variable temperature and different concentration, DLS, AFM and SEM imaging) confirm the self -aggregation process of these dendrimers, despite the butterfly-like shape of the exTTF units, highly distorted from planarity, to form large supramolecular architectures in the gas phase, in solution, and on a mica surface. Dendrimers 5, 9, and 12 host a number of C-60 molecules to form segregated arrays of donor and acceptor units which could give rise to valuable materials useful for the preparation of optoelectronic devices. UV-vis fitration experiments demonstrate that complexation of C-60 occurs in a positive cooperative manner. Cyclic voltammetry experiments show that the peripheral exTTF units are involved in multioxidation processes. The self-diffusion coefficients (D) of the dendrimers reported herein and the previously reported exTTF (1) and tweezer (2) have been calculated from their chronoamperograms at different concentrations and by the Cottrell equation and, where possible, by PFG-NMR. The calculated values for D demonstrate the decrease of this magnitude with increasing dendrimer size.