A copper-catalyzed novel, highly selective formamide (NÀ H) activation for the accessing broad range of formamide sulfides was developed. This strategy presented the first example on NÀ SÀ N bonds construction under mild conditions, featuring selective N-radical based mechanism, as well as cheap, stable and environmentally friendly S 8 as source of sulfur. In particular, this process was well defined by DFT calculation and a leading product was found to have significant anti-fungal activity.