Trifluoromethylthiolative difunctionalization of alkenes, a cheap and abundant feedstock, which installs a trifluoromethylthiol (SCF₃) group and another unique functional group across the carbon–carbon double bonds, provides an ideal strategy for the preparation of β-functionalized alkyl trifluoromethyl sulfides and has become a hot topic recently. This review aims to summarize the major progress in this exciting research area, with particular emphasis on the mechanistic aspects of the reaction pathways.