Herein, we report a rare example of trapping arynes using in situ generated aryltrifluoromethylnitrone to access an important class of trifluoromethylated benzoxazolines. This three-component strategy involves a nitrone formation/[3 + 2] cycloaddition/thermal rearrangement cascade and furnishes trifluoromethylated benzoxazolines in high yields. The scope of the reaction is quite broad with respect to aryltrifluorodiazoethanes, nitrosoarenes, and arynes. The proposed reaction pathway is supported through the isolation and characterization of the key reaction intermediates phenyltrifluoromethylnitrone and benzisoxazoline.