A fluorinative Beckmann fragmentation of α-oximinoamides was devised to provide synthetically useful carbamoyl fluorides. High selectivity for fragmentation over a potentially competing Beckmann rearrangement was observed. This protocol has a distinct mechanism and thus a different substrate scope compared with other synthetic methods. α-Oximinoamides derived from the readily available secondary amines, lactams, or isatins were converted into structurally diverse carbamoyl fluorides.