Bulky biaryl phosphine ligands facilitate Pd-catalyzed C−O coupling reactions of aryl halideswith primary and secondary alcohols by promoting reductive elimination at the expense of β-hydrideelimination. The key to their success is the ability to match the size of the ligand to that of the combinationof substrates. The efficient coupling of a number of unactivated aryl chlorides and bromides with cyclicand acyclic secondary alcohols was achieved. This included the coupling of allylic alcohols for the firsttime in a Pd-catalyzed coupling process.