A series of donor–acceptor -, -, and rotaxanes and self-complexes (rotaxanes) have been synthesized by a threading-followed-by-stoppering approach, in which the precursor pseudorotaxanes are fixed by using CuI-catalyzed Huisgen 1,3-dipolar cycloaddition to attach the required stoppers. This alternative approach to forming rotaxanes of the donor–acceptor type, in which the donor is a 1,5-dioxynaphthalene unit and the acceptor is the tetracationic cyclophane cyclobis(paraquat-p-phenylene), proceeds with enhanced yields relative to the tried and tested synthetic strategies, which involve the clipping of the cyclophane around a preformed dumbbell containing π-electron-donating recognition sites. The new synthetic approach is amenable to application to highly convergent sequences. To extend the scope of this reaction, we constructed rotaxanes in which one of the phenylene rings of the tetracationic cyclophane is perfluorinated, a feature which significantly weakens its association with π-electron-rich guests. The activation barrier for the shuttling of the cyclophane over a spacer containing two triazole rings was determined to be (15.5±0.1) kcal mol−1 for a degenerate two-station rotaxane, a value similar to that previously measured for analogous degenerate compounds containing aromatic or ethylene glycol spacers. The triazole rings do not seem to perturb the shuttling process significantly; this property bodes well for their future incorporation into bistable molecular switches.