Aromatic hydrogenation is a challenging transformation typically requiring alkali or transition metal reagents and/or harsh conditions to facilitate the process. In sharp contrast, the aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene is shown to be reduced under 4 atm of H2 to give [3.1.0]bicylo reduction products, with the struc-ture of the major isomer being confirmed by X-ray crystal-lography. NMR studies show this reaction proceeds via a reversible 1,4-H2 addition to generate an intermediate species, which undergoes an irreversible suprafacial hydride shift concurrent with P-P bond formation to give the isolated product. Further, para-hydrogen experiments confirmed the addition of H2 to triphosphabenzene is an intramolecular process. DFT calculations show that facile distortion of the planar triphosphabenzene towards a boat-conformation provides suprafacial combination of vacant acceptor and donor orbitals that permits this direct and uncatalyzed re-duction of the aromatic molecule.