A novel S-induced Schmidt-type rearrangement of vinyl azides with CF₃SO₂Na is reported, which is mediated by triphosgene (BTC) under mild reaction conditions. A wide range of N-arylated 2-(trifluoromethylsulfinyl)acetamides, for the first time, were successfully obtained in good yields, through sequential trifluoromethylsulfinylation and aryl 1,2-migration.