Reaction of 1,1'-bis(diphenylphosphino)binaphthol (BINAPO, 1) with [RuCl₂(η⁶-arene)]₂ in methanol leads to dinuclear BINAPO-bridged Ru compounds [{RuCl₂(η⁶-p-cymene)}₂-(μ-BINAPO)], 2a, in near quantitative yield. In dichloromethane or acetonitrile, 1 preferably affords mononuclear species in which one of the phosphine centers remains uncoordinated. These complexes can be further stabilized by reaction with BH₃ to afford, for example, [RuCl₂(η⁶-p-cymene)(η¹-BINAPO-BH₃)], 4a. Upon heating a mixture of 1 and RuCl₂(η⁶-p-cymene) in DMF, P-O bond cleavage occurs to afford [RuCl(η²-PPh₂-BINOL)(η⁶-p-cymene)], 5a, bearing an anionic PO-chelating ligand. Ligand 1 acts as an intact chelate when reacted with [Ru₂(μ-Cl)₃(η⁶-p-cymene)₂][PF₆] to yield [RuCl(η⁶-p-cymene)(η²-BINAPO)][PF₆], 7. Reaction of 1 with [RuCp(CH₃CN)₃] [PF₆] in acetonitrile or chloroform affords [{RuCp(CH₃CN)₂}₂(μ-BINAPO)][PF₆]₂, 8, and [RuCp(CH₃CN)(η² -BINAPO)][PF₆], 9, respectively. The solid-state structures of 1, 2a, 4a, and 7 are reported, that of 2a representing a rare structural example of a molecule with a bridging binaphthyl-type ligand.