A practical and efficient method for the N-acrylation of amines with (trifluoromethyl)alkenes is achieved via the cleavage of three C(sp3)-F bonds, affording a diverse range of useful tertiary and secondary α-arylacrylamides in high yields. This protocol features mild conditions, is transition-metal free, operationally simple, gram-scalable, and compatible with valuable functional groups, and has a broad substrate scope. Mechanistic studies indicate that exchange of an oxygen atom happens between H2O and NaOH, and that the oxygen atom is incorporated into the α-arylacrylamides via the ipso-defluorooxylation of the (trifluoromethyl)alkene. This method is also applied in the late-stage N-acrylation of pharmaceuticals.