Molecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional systems. Herein, we report on the synthesis, characterization, and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox(4+), containing a diazaperopyrenium (DAPP(2+)) unit and an extended viologen (ExBIPY(2+)) unit, which are linked together by two p-xylylene bridges. Both H-1 NMR spectroscopy and single-crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox(4+). The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif; leading to two types of pi center dot center dot center dot pi interactions: (i) between the ExBIPY(2+) unit and the DAPP(2+) unit (pi center dot center dot center dot pi distance of 3.7 angstrom) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY(2+) unit (pi center dot center dot center dot pi distance of 3.2 angstrom) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox(4+) at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the (1)*ExBIPY(2+) unit to the DAPP(2+) unit in 0.5 ps to yield (1)*DAPP(2+). The same excitation wavelength simultaneously populates a higher excited state of 1*DAPP(2+) which then undergoes ultrafast intramolecular electron transfer from 1*DAPP(2+) to ExBIPY(2+) to yield the DAPP(3+center dot)-ExBIPY(+center dot) radical ion pair in tau = 1.5 ps. Selective excitation of DAPP(2+) at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.