A series of new pi-stacked compounds, 1,8-bis(2',5'-dimethoxybenzene-1'-yl)aphthalene (1), 1,4-bis(8'-(2 '',5 ''-dimethoxybenzene-1 ''-yl)naphthalen-1'-yl)benzene (2), and 1,8-bis(4'-(8 ''-(2"',5"'-dimethoxybenzene-1"'-yl)naphthalen-1 ''-yl)-benzene-1'-yl)naphthalene (3), have been synthesized and characterized herein as precursor molecules of monocationic mixed-valence systems (MVSs). The three-dimensional geometries of these compounds were determined by X-ray crystallography. A near-orthogonal alignment of the naphthalene pillaring motif to the dimethoxybenzene redox center, or the phenylene spacer, imposes cofacial alignment of these units in a juxtaposed manner with sub-van der Waals interplanar distances. Cyclic and differential pulse voltammograms reveal that the Delta E values between two sequential oxidation potentials are 0.30, 0.11, and 0.10 V for 1, 2, and 3, respectively. MVSs derived from these compounds are recognized as class II according to the Robin and Day classification. The decay parameter beta, which describes the distance dependence of the squared electronic coupling in the three mixed-valence systems, was experimentally determined via Mulliken-Hush analysis of the intervalence charge transfer band (beta = 0.37 angstrom(-1)) and theoretically assessed from charge-resonance contributions derived from DFT computations (beta = 0.37 angstrom(-1)). These values are extraordinarily mild, indicating that the electronic interaction between redox centers in the longitudinal direction may be comparable to that in the transverse direction, if the MVS system is appropriately designed.