Abstract We report a ligand‐to‐metal charge‐transfer (LMCT) process that used ferric (III) chloride as efficient chlorination reagent to mediate the vicinal dichlorination of alkenes. Under 420 nm LED light, the easily available and safe ferric (III) chloride could facilitate various alkenes to transform as 1,2‐dichloride compounds with good to excellent yields (19 examples). The strategy showed a more economic protocol than CuCl 2 , and provided a significant reference for the light‐Induced dichlorination in industrial catalysis.