Herein, we report an unprecedented mixed-valence crystal superstructure that consists of a 2:1 host-guest complex [MV subset of(CBPQT)(2)](2/3+) [MV = methyl viologen, CBPQT = cyclobis(paraquat-p-phenylene)]. One electron is distributed statistically between three [MV subset of(CBPQT)(2)](center dot+) composed of a total of 15 viologen units. The mixed-valence state is validated by single-crystal X-ray crystallography, which supports an empirical formula of [MV subset of(CBPQT)(2)](3)center dot(PF6)(2) for the body-centered cubic superstructure. Electron paramagnetic resonance provides further evidence of electron delocalization. Quantum chemistry calculations confirm the mixed-valence state in the crystal superstructure. Our findings demonstrate that precise tuning of the redox states in host-guest systems can lead to a promising supramolecular strategy for achieving long-range electron delocalization in solid-state devices.