Our initial investigation began with benzene (1a) as the model substrate (Table ). After extensive screening of conditions, we found that when using 1 equivalent of pyridinium fluoroborate reagent (PNSF, 2a, E1/2 red = -0.48 V vs SCE), 2 mol% of fac-Ir(ppy)3, 10 equivalents of benzene in DCM (dichloromethane):DCE (1,2-dichloroethane) = 1:1 (2.0 mL) under the irradiation of 30 W blue LEDs, the phenylsulfamoyl fluoride product 3a could be obtained in 72% yield. Different solvents were then examined (Table ). When other solvents were used, the yield of 3a was distributed in 4% to 71% (entry 2). Next, different benzene equivalents were investigated (entry 3), and the results revealed that lowering the benzene equivalents would lead to a decrease in the yield of 3a (only for volatile arenes, for nonvolatile substrates, see supplementary information for more details). The results of orthogonal screening of photocatalysts, light sources, and solvents have shown that the proper combination of photocatalysts and mixed solvents is critical (entries 4-7), when using 1 equivalent of PNSF-2a, 2 mol% of fac-Ir(d-F(p-t-Bu)ppy)3, 10 equivalents of benzene in DCM:MA (Methyl acetate) = 1:1 (2.0 mL) under the irradiation of 30 W blue LEDs, the phenylsulfamoyl fluoride product 3a could be obtained in 91% yield. Furthermore, control experiments suggested that photocatalyst, and light irradiation are all crucial to the reaction (entries 8-9).