Ni-catalyzed intermolecular allylic dearomatization reaction of β-naphthols with allylic alcohols was achieved. By utilizing Ni(cod)2 as a catalyst precursor, DPEphos as a ligand and 4 Å molecular sieves as additives, the dearomatization reaction of β-naphthols with aryl allylic alcohols proceeded smoothly under mild conditions, affording the desired β-naphthalenone products bearing a quaternary carbon center in moderate to good yields with excellent linear selectivity.