In 2017 Garg stated about arynes that "their high reactivity has seemingly steered chemists away from using them to assemble […] complex scaffolds. [But] arynes can and should be used strategically to enable the synthesis of complex molecules with motifs that have conventionally been viewed as challenging." In the present paper, we meet this suggestion by introducing the aryne phosphate reaction that accesses highly challenging arylated organophosphorous compounds with Kobayashi-type precursors. We demonstrate that inorganic phosphates, organophosphates and cyclophosphates are efficient arynophiles in O-arylation reactions. An extensive portfolio of products was presented, ranging from arylmonophosphates and -diphosphates to arylphosphodiesters and -polyphosphates. Yet, there are countless more combinations that can be envisioned to further expand the repertoire of the aryne phosphate reaction. The versatility of this novel transformation is further demonstrated by synthetically unlocking penta-, hepta-and octaphosphorylations in one-flask operations. Polyphosphorylation reagents introducing defined phosphate chains with more than four units in a single reaction have never been reported before. Consequently, the disclosed penta-, hepta-and octaphosphorylation procedures set new benchmarks in polyphosphorylation chemistry. It is apparent that longer polyP chains could potentially be accessible by either extending the ring-size or by using phosphate nucleophiles on arylated cyclophosphates. We are confident that the aryne phosphate reaction will stimulate tool design in nucleotide and polyP research and -more generally -enable us to venture into the largely uncharted and fascinating realm of condensed phosphates.