An innovative one-step synthesis towards β-aryl-β,β-difluorocarbamates and β-aryl-β,β-difluoroazides is presented. The described approach relies on the use of α-fluorostyrene substrates in a radical addition/fluorination reaction with N-centered radicals in the presence of Selectfluor®. The best results were obtained for the azidofluorination reaction. The resultant β-arylβ,β-difluoroazides were further transformed into Nitrogenbased heterocycles (e. g. pyrrole, triazole, and tetrazole) and in more elaborated azide derivatives.