[reaction: see text] Air-stable and easily accessible PinP(O)H enables highly efficient palladium-catalyzed Kumada cross-coupling reactions of aryl tosylates. The in situ generated catalyst proved applicable not only to electron-rich and electron-poor carbocyclic tosylates but also to heterocyclic tosylates, such as pyridine and quinoline derivatives. The results described herein constitute the first use of air-stable secondary phosphine oxides as preligands for transition-metal-catalyzed coupling reactions between organometallic species and tosylates.