In our consideration of this approach and previous report, 14 we envisioned that aryl sulfonate salts have low redox potentials (E1/2 = -0.37 V vs. SCE in CH3CN) and could undergo single electron transfer oxidation by photogenerated hole form excited g-CN which is effective to generate sulfonyl radicals. Oxidative addition of Ni(0) species to an aryl halide delivers the Ni(II) intermediate 14 which tends to trap the sulfonyl radicals yielding a Ni(III) organometallic adduct. Subsequent reductive elimination produces the targeted C(sp 2 )-SO2Ar cross-coupling product. Finally, the electron form semiconductor surface is utilized for the reduction of the Ni(I) species to Ni(0) species through another single electron transfer to complete the whole Ni catalytic cycle (Scheme 1c). Scheme 1. Significant of Sulfones and Experimental Design With this design in mind, we began to investigate the possibility and figure out the best conditions primarily. According to Table , 4-bromotoluene 1a and sodium benzene sulfinates 2a were chosen to be the model substrate separately. To our delight, the product 1-methyl-4-(phenylsulfonyl) benzene 3a was obtained with the excellent yield of up to 82% under 45W blue led (455 nm) irradiation and 10 wt% of g-CN, (Synthesis method was shown in Support information, SI), 5 mol% NiBr2•DME and 10 mol% L1 added in DMF as the standard condition (entry 1). Then, the reaction could not happen when the absence of light, g-CN, or nickel catalyst respectively (entry 2). We chose the Ni(COD)2 as the nickel source but a modest yield was acquired (entry 3). Meanwhile, we also investigated the ligand effect to this reaction system. Firstly, when no ligand was involved, the produced 3a could not be observed at all (entry 4), and then we changed similar ligands such as L2 or L3, but an unsatisfactory result (entry 5, 6) was shown. MeCN, MeOH or acetone was selected to be solvent respectively, but trace product was detected (entry 7). Shortening reaction time to 12 h, the yield was decreased to 68% accordingly (entry 8). The reaction could not be occurred without degassing (entry 9). Under the same conditions, chlorobenzene was introduced but no results were obtained. Considering the difficulty of oxidation addition between Ni complex and chlorinated benzene, so we attempted to raise the temperature to 60 o C, in that case, 12% yield of product was observed finally, and we also chose the iodobenzene as the substrate which obtained 3a up to 78% yield (entry 10).