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Using visible light as energy to form free radicals has important synthetic value. A novel and efficient visible-light-mediated strategy has been developed for the generation of thiobenzene radicals through cerium-catalyzed activation of the disulfides. Through this photochemical reaction, various 3-sulfenylated quinoxalin-2(1H)-ones can be conveniently obtained in good yields with good functional group tolerance. Our transformation provides an alternative that allows rapid access to various C3 sulfenylated quinoxalin-2(1H)-ones in a sustainable and practical manner.