The reaction of thiocarbonyl fluoride, generated from difluorocarbene, with various amines under mild conditions is described. Secondary amines, primary amines, and o‐phenylenediamines are converted to thiocarbamoyl fluorides, isothiocyanates, and difluoromethylthiolated heterocycles, respectively. Thiocarbamoyl fluorides were further transformed into trifluoromethylated amines by using a one‐pot process. Thiocarbonyl fluoride is generated in situ and is rapidly fully converted in one pot under mild conditions; therefore, no special safety precautions are needed. Stay safe: The reaction of thiocarbonyl fluoride, generated from difluorocarbene, with various amines proceeded smoothly under mild conditions to give thiocarbamoyl fluorides, isothiocyanates, and difluoromethylthiolated heterocycles. Thiocarbonyl fluoride is generated in situ and no special safety precautions are needed.