Abstract An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF 3 and nBu 4 NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF 3 /nBu 4 NI. This protocol is tolerant of different functional groups and might be applicable to late‐stage trifluoromethylthiolation of alcohols.