Abstract Various 2-[Ar (alk) ylsulfonyl] ethanols were prepared and subsequently converted into the corresponding phosphorodichloridites in almost quantitative yield via a convenient synthetic route. The versatility of the method, which obviates the necessity of a distillation step, is demonstrated by the preparation of other Ar (alk) yl phosphorodichloridites, including the unstable benzyl phosphorodichloridite.