A series of novel trifluoromethylative thiolations of alkene are realized by using visible light as a driving force and iron salts as a catalyst, and 1,2-bis(trifluoromethylated) compounds could be obtained in moderate to good yields. These multicomponent protocols proceed in an atom-economical way with a broad substrate scope. Biologically active chemicals can also be tolerated to provide desired products, suggesting that the catalytic protocol could be viable for late-stage modification in pharmaceutical discovery. At last, flow-setup synthesis of the desired product is successfully applied on a gram scale, indicating the synthetic power of these reactions in industrial applications.