The direct trifluoromethylthiolation of aziridines with AgSCF3 and iodides is reported. The β-trifluoromethylthiolated isothiocyanates and amines were selectively obtained by the changed cation of iodide. This strategy is tolerant to a wide range of functional groups with good yields and regioselectivities. In addition, the isothiocyanates can be used for further synthetic manipulation, which offered a convenient approach for SCF3-containing compounds.