On the ground of advanced electrochemical, spectroscopic and theoretical data, we have demonstrated that two bipyridinium radicals introduced on the lower rim of a calixarene skeleton can be efficiently and reversibly pi-dimerized. A detailed electrochemical investigation supports the conclusion that the non-covalent association between both electrogenerated radical-cations proceeds intramolecularly with a fast kinetics, the electrochemical behaviour being mostly limited, in the accessible scan range, by the kinetics of the heterogeneous electron transfer. Further insights into the structure and stability of a series of covalently linked pi-dimers have been provided by DFT calculations carried out at various computational levels. A major result of these theoretical investigations is that solvents and dispersion-correcting potentials have to be considered to accurately model the non-covalent interactions involved in pi-dimer complexes.