A visible-light photoredox-catalyzed difunctionalization of diazomethyl radicals with two heteroatomic nucleophiles (saturated bonds) generated in situ from the reaction of secondary amines with CS 2 or CO 2 has been developed for the first time. This reaction provides a new and modular approach for the synthesis of valuable but difficultly accessible S-alkyl di-dithiocarbamates and O-alkyl di-carbamates from readily available starting materials in a single step.