To date, three methods have been mainly used to construct stacked structures. First, by introducing functional groups and/or side chains into -conjugated molecules with a wide -plane, attractive interaction between molecules can induce aggregation, where the formation of aggregates is more enthalpically favorable in the crystalline state or under conditions of high concentration and low temperature. Second, by the inclusion of two or more -conjugated molecules in a cage-shaped molecule, molecules are forced to be stacked and interact with each other. Third, by using cyclophanetype structures with two or more linkers, the -planes are forced to be closely arranged and form a faceto-face stacked structure. Among them, we considered that cyclophane-type structures are suitable for realizing the stacking of cationic -systems because the other two approaches would be less promising due to electrostatic repulsion between cationic units. We envisaged that, by stacking of the cationic units, considerable changes in color (e.g., blue-or red-shift) and reduction behavior (e.g., stepwise one-electron reduction) would be expected compared to the results with the corresponding monomeric cation. Thus, we designed cyclophane-type dications 2 2+ with coplanar xanthylium units, which would have a stacked geometry of reference monocations 1 + (Figure ). In this study, we investigated the effect of the cyclophane-type structure on the physical properties and redox behavior of 2 2+ . Due to the close proximity of cationic units realized by the above molecular design, the intramolecular interaction between cation units enables a change in absorption. Furthermore, this cation-stacking approach can stabilize their reduced species, allowing us to observe clean electrochromic behavior, even though the reduced states are open-shell species.