Because of their high reactivity and short lifetime, arynes are commonly generated in situ from stable precursors. Many strategies for aryne synthesis are available, and Kobayashiprecursors based on the o-silylaryltriflate functionality are particularly well developed. In this approach, fluoride ions induce aryne formation from bench-stable precursors in a temperature range in between 0 °C to 100 °C. Arylated organophosphorous compounds are important building blocks in organic synthesis including various applications in medicinal chemistry, polymer science or as ligands in transition metal catalysis. Aryne-based methodologies have played a significant role in targeting such aryl-phosphorous compounds (scheme 1, A). In 2010, Jugé et al. presented a nucleophilic addition of phosphines to arynes leading to arylphosphonium salts (3). Biju and He demonstrated later in 2014 and 2016 how this reactivity can be applied in multicomponent reactions with carbonyls or CO2. Furthermore, Studer, Daugulis, and Miura developed aryne induced σ-P III -X bond insertions accessing ortho-stannylated, silylated or phosphinylated arylphosphines (6). Analogously, Alajarin and Gogoi presented π-P V =X bond insertions leading to ortho-aminated, thiolated or hydroxylated arylphosphonium products (8). Between 2013 and 2021 Mhaske, Chen and Willoughby applied phosphites, H-phosphonates and silylphosphates (11) to generate arylphosphonates (12). Moreover, He presented a σ-P-O-bond insertion of arynes into organophosphinic acids (9). In summary, the broad spectrum of aryne reactivity can be exploited with phosphorous functionalities towards diversely arylated products enabling C-P -bond formation. However, no exclusive aryne-based Oarylation has ever been described in the synthesis of organophosphorous compounds. More generally, "there are limited examples of O-arylation transformations" using arynes (scheme 1, B), overall restricted to few hydroxyl and carboxylgroup arylation protocols since 2004. Despite the many studies scrutinizing the reactivity of diverse arynophiles, the ability of phosphates to engage in reactions with arynes is absent from the literature. This is remarkable, as the urgent need to access probes for interrogation of phosphate functions, e.g. in analytical biochemistry, has driven innovative synthesis strategy development in the past years. Scheme 1. A: Previously reported aryne chemistry of organophosphorous compounds based on o-silylphenyltriflates. B: Previously reported O-arylation chemistry of arynes based on o-silylaryltriflates. C: Synthetic concept of the aryne phosphate reaction including potentially accessible product groups.