Abstract Aryl alcohols are employed as feedstock for the Heck reaction. Keggin-type heteropolyacids catalyse the selective dehydration of the alcohols to styrenes, which, in one- pot, undergo palladium-catalysed Heck arylation with aryl bromides, affording broadly functionalised stilbenes. The choice of solvent is critical for the cascade dehydration–Heck reaction, with electron-rich aryl alcohols preferring a basic medium while electron- ...