The synthesis and characterization of two new (TTF-DNP-CBPQT4+) rotaxanes 1 and 2 is reported, based on tetrathiafulvalene (TTF), 1,5-dioxynaphthalene (DNP), and cyclobis(paraquat-p-phenylene) (CBPQT4+) with cyclohexyl and alkyl chains as the spacers. Multilayer Langmuir–Blodgett (LB) films of rotaxanes 1 and 2 are prepared. Conducting atomic force microscopy, scanning tunneling microscopy, and two-terminal junction device studies indicate that the LB films of rotaxanes 1 and 2 show electrical bistability behavior. By comparing with the TTF-DNP-CBPQT4+ rotaxanes reported by Stoddart et al. previously, the present results imply that proper modification of the chemical structures of the TTF unit and the spacer have negligible effect on the electrical bistability behavior of these TTF-DNP-CBPQT4+ rotaxanes. These findings will allow for the design and preparation of new multifunctional TTF-DNP-CBPQT4+ rotaxanes in the future.