In this study, we obtained the first cation radical solid of a highly symmetric (D6h) polyaromatic hydrocarbon, coronene, by electrooxidation. The (coronene)3Mo6Cl14 salt, which is formed with an Oh-symmetric molybdenum cluster unit Mo6Cl142–, has an isotropic cubic structure with Pmm symmetry. The presence of two orientations for the coronene molecules related by an in-plane 90° rotation (merohedral disorder) allows for fourfold symmetry along the <100> direction. The disorder has dynamic features because 2H NMR spectroscopic studies revealed that the coronene molecules undergo an in-plane flipping motion. The observation of two motional sites with significantly different rotational rates (300 Hz and 5 MHz at 103 K) in an approximate 2:1 ratio appears to be consistent with the splitting of a Raman-active A1g mode, confirming a random charge-disproportionated state instead of a uniform partially-charged state. The slower- and faster-rotating species are assigned to charge-rich and charge-poor coronenes, respectively, with respect to C–H···Cl hydrogen bonds with neighboring Mo6Cl142– cluster units. The electrical conductivity of the salt is rather high but is well-described by a three-dimensional (3D) variable-range hopping mechanism, which is possibly associated with the random charge disproportionation. These results provide a significant step forward in developing an isotropic 3D π-conducting system composed of planar π-conjugated molecules.