The classical route to the PMe₃-stabilised polycyclic aromatic hydrocarbon (PAH)-substituted diborenes B₂Ar₂(PMe₃)₂ (Ar = 9-phenanthryl 7-Phen; Ar = 1-pyrenyl 7-Pyr) via the corresponding 1,2-diaryl-1,2-dimethoxydiborane(4) precursors, B₂Ar₂(OMe)₂, is marred by the systematic decomposition of the latter to BAr(OMe)₂ during reaction workup. Calculations suggest this results from the absence of a second ortho-substituent on the boron-bound aryl rings, which enables their free rotation and exposes the B–B bond to nucleophilic attack. 7-Phen and 7-Pyr are obtained by the reduction of the corresponding 1,2-diaryl-1,2-dichlorodiborane precursors, B₂Ar₂Cl₂(PMe₃)₂, obtained from the SMe₂ adducts, which are synthesised by direct NMe₂–Cl exchange at B₂Ar₂(NMe₂)₂ with (Me₂S)BCl₃. The low-lying π* molecular orbitals (MOs) located on the PAH substituents of 7-Phen and 7-Pyr intercalate between the B–B-based π and π* MOs, leading to a relatively small HOMO–LUMO gap of 3.20 and 2.72 eV, respectively. Under vacuum or at high temperature 7-Phen and 7-Pyr undergo intramolecular hydroarylation of the BB bond to yield 1,2-dihydronaphtho[1,8-cd][1,2]diborole derivatives. Hydrogenation of 7-Phen, 7-Pyr and their 9-anthryl and mesityl analogues III and II, respectively, results in all cases in splitting of the B–B bond and isolation of the monoboranes (Me₃P)BArH₂. NMR-spectroscopic monitoring of the reactions, solid-state structures of isolated reaction intermediates and computational mechanistic analyses show that the hydrogenation of the three PAH-substituted diborenes proceeds via a different pathway to that of the dimesityldiborene. Rather than occurring exclusively at the B–B bond, hydrogenation of 7-Ar and III proceeds via a hydroarylated intermediate, which undergoes one B–B bond-centered H₂ addition, followed by hydrogenation of the endocyclic B–C bond resulting from hydroarylation, making the latter effectively reversible.