excellent selectivity. In the cases of aliphatic isocyanides (RCN), a novel diselenide-assisted bisthiolation of RNC with diaryl disulfides (Ar‘SSAr‘) proceeds successfully to give the corresponding bisthiolation products (Ar‘S−C(NR)−SAr‘), although the same photoirradiated reaction of RNC with diaryl disulfides does not occur in the absence of diselenide. These double chalcogenation reactions are assumed