In recent years, organic open-shell molecules have drawn increasing attention from both fundamental and applied aspects, because they show unique structural electronic features and spin-nature-based functionalities that are intrinsically different from closed-shell molecules. [1][2][3][4] The latest trends are exemplified in chemical entities affording dynamic nuclear polarization to give rise to enormous sensitivity enhancement in biological NMR spectroscopy [3] and the use of molecular electron spins as synthetic spin quantum bits (qubits) for quantum information science and quantum computers (QCs). [4] The latest progress in molecular spin science has been underlain by the design and synthesis of airstable organic open-shell molecules. [1] Phenalenyl (PLY in Scheme 1) is an odd-alternant carboncentered neutral p radical with a high thermodynamic stability arising from delocalization of an unpaired electron over the planar D 3h -symmetric 13p-electron system. However, owing to a kinetic instability, in solution, PLY gradually decomposes to peropyrene, a closed-shell polycyclic hydrocarbon, through s dimerization even under oxygen-free conditions. [5] Introduction of tert-butyl groups into the phenalenyl skeleton allowed us to isolate, for the first time, TBPLY (Scheme 1) in its crystalline state. [6] Since then, by using the steric protection effect of bulky substituents, several kinds of air-stable phenalenyl derivatives were synthesized and isolated, all of which have exotic structures and properties owing to the extensively spin-delocalized nature of the phenalenyl system. [7][8][9] Efforts have been made to synthesize electronically stabilized phenalenyl systems by introducing heteroatom functional groups, such as alkoxy, [10a-c, 11a] amino, [10b-d] thio, [11] and cyano [10a, 12] substituents at the peripheral carbon atoms. These phenalenyl radicals are important to understand electronic perturbation effects and intermolecular interactions attributable to the introduced heteroatom substituents in solids. However, detailed investigations in this context, particularly relevant to the electronic-spin properties, have rarely been reported except for thio-or cyanosubstituted radicals, [11a, 12] owing to the intrinsic kinetic instability of the neutral radical species. [13] Here we report the synthesis, electronic-spin structure, and novel spin-based quantum coherence of the hexamethoxylphenalenyl neutral p radical 1C (Scheme 1), in which the coherence is related to a large number of equivalent nuclear spins. Interestingly, the symmetrical introduction of six methoxy groups into the phenalenyl skeleton played a crucial role not only to electronically stabilize the radical species 1C by the resonance effect, [14] but also to provide extremely wellresolved ESR hyperfine splittings with a very small linewidth in solution associated with temperature-dependent dynamic behavior of spin angular momenta in molecular frames. This unique hyperfine spectroscopic feature allowed us to investigate spin-based quantum na...