An efficient, metal‐free C–H halogenated method for the synthesis of β‐halogenated carboxamides using non‐corrosive NXS (X=Cl, Br) as the halogenated source and ammonium sulfocyanide (NH4SCN) as the additive was proposed and accomplished. Various substituted 2‐oxazolines efficiently afforded the corresponding β‐halogenated carboxamides via a ring‐opening reaction in good yields. The characteristic features of this reaction include readily available materials, mild reaction conditions and functional groups tolerance. [ABSTRACT FROM AUTHOR]