Encouraged by the prospect of producing an electrochemical, color-switchable red–green–blue (RGB) dye compound, we have designed, synthesized, and characterized two three-station catenanes. Both are composed of macrocyclic polyethers containing three π-electron-rich stations, which act as recognition sites for a π-electron-deficient tetracationic cyclophane. The molecular structures of the two three-station catenanes were characterized fully by mass spectrometry and 1H NMR spectroscopy. To anticipate the relative occupancies of the three stations in each catenane by the cyclophane, model compounds with the same constitutions in the vicinity of the stations were synthesized. The relative ground-state populations of the three stations occupied in both catenanes were estimated from the thermodynamic parameters for 1:1 complexes between all these model compounds and the cyclophane, obtained from isothermal titration calorimetry (ITC). The electrochemical and electromechanical properties of the three-station catenanes were analyzed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and spectroelectrochemistry (SEC). The first three-station catenane was found to behave like a bistable system, whereas the second can be described as a quasi-tristable system.