In conclusion, we have successfully developed a photocatalytic hydroarylation protocol that efficiently targets the Dha-backbone utilizing versatile arylthianthrenium salts. This novel strategy has demonstrated its versatility in synthesizing a diverse array of unnatural amino acids, with the potential for straightforward scale-up under a continuous-flow regime. The remarkable functional group tolerance of our methodology enables the preservation of delicate chemical structures during synthesis, broadening the scope of compatible coupling partners.