We have developed a visible-light-induced COCl2 generation method using CHCl3 and sodium chlorite as the starting materials, which are inexpensive and easy to handle. Various carbamoyl chlorides can be synthesized safely and efficiently via the phosgenation reactions of amines using COCl2 generated in situ. This is an excellent method that can be applied to a wide range of substrates, including anilines and aliphatic amines, as well as pharmaceutical compounds with nucleophilic nitrogen atoms. In addition, this phosgenation method was successfully applied to carbonate synthesis from phenols and alcohols. This novel phosgenation system is an alternative to the classical method that involves the use of a hazardous reagent.