A series of gem-chlorosulfurization products bearing difluoromethyl substituents were synthesized in high to excellent yields directly from p-toluenesulfonyl difluorodiazoethane (TsCF2CHN2), disulfides and PhICl2 without any catalysts or additives. The mild reaction conditions and high functional group compatibility indicated the utility and sustainability of the method. In addition, the gem-chlorosulfurization products could be efficiently converted to sulfur-containing and aryl substituted difluoromethyl derivatives by a feasible multi-component operation.