Abstract A solvent-controlled divergent thiocyanation of carbazoles and di/triphenylamines has been developed. Using either CH3CN/H2O (3:1) or DMSO as the solvent, a facile and efficient protocol for the solvent-controlled divergent synthesis of mono- and di-thiocyanation of carbazoles and di/triphenylamines was achieved. The salient features of this transformation include simple and mild reaction conditions, easily available substrates, and broad substrate scope.