The new ambiphilic ligand Ph2P–(1,1′-ferrocenyl)–BMes2, prepared by sequential lithiation/electrophilic trapping of 1,1′-dibromoferrocene, adopts a monomeric structure free of dative P → B and Fe → B interactions. This flexible phosphine-borane and the related o-phenylene bridged system have been evaluated in Rh-catalyzed hydroformylation.