Two donor-acceptor thread-like compds. incorporating viologen (V2+) units and 1,5-dihydroxynaphthalene (DNP) stations have been prepd. Their ability to form self-assembled charge-transfer (CT) complexes with cucurbituril (CB) is evidenced by UV-Vis and NMR spectroscopies, as well as by mass spectrometry. Binding studies show the formation of 1 : 1 and 2 : 1 complexes between CB and a thread-like compd. contg. two viologen units, while only a 1 : 1 inclusion complex was obsd. between CB and a thread-like compd. contg. only a single viologen unit. The switching behavior of the threads within their pseudorotaxane frameworks was investigated by using cyclic voltammetry (CV) and UV-Vis spectroscopy.