A novel strategy of bisphosphorylation of anhydrides with P(O)-H reagents via a DMAP-catalyzed and DBU-promoted process has been developed. These one-step transformations proceed efficiently to provide convenient access to a variety of P-O-C-P motif containing organophosphorus compounds. In addition, the gram-scale synthesis and the efficient recovery of the by-product highlight the sustainability and applicability of this method.