A calixarene wheel, whose cavity has been extended and rigidified by N-phenylureido groups on the upper rim, forms pseudorotaxane species with molecular axles containing the viologen (4,4¢- bipyridinium) unit in CH2Cl2 solution. In these conditions, the self-assembly process is very efficient, with associated ¢G° values of around -8 kcal mol-1. The counteranions of the bipyridinium-based threads play indeed an important role in the formation of the complex. The use of either tosylate or hexafluorophosphate salts of the guests affects both the stability of the complexes and the rate of the threading process. Such effects have been interpreted in terms of ionpair recognition, suggesting that coordination of the counteranions of the viologen thread by the ureido groups of the calixarene wheel is crucial for the breaking of tight ion pairs prior to threading. The rate constants of the threading/dethreading reactions coupled with the redox processes of the viologen unit of the axle have been obtained by means of cyclic voltammetry. The pseudorotaxane species undergo fast dethreading (submicrosecond time scale) on electrochemical reduction of the guest. The heterogeneous electron-transfer kinetics for the reduction of the viologen unit is slowed upon encapsulation into the calixarene cavity.