An efficient and straightforward synthesis of polysubstituted oxazol-2­(3H)-ones has been developed via a tandem Hofmann-type rearrangement and cyclization reaction of various α-acyl-β-aminoacrylamides mediated by phenyl iodine­(III) bis­(trifluoroacetate) (PIFA) in the presence of trifloroacetic acid (TFA). This novel protocol features readily available starting materials, mild reaction conditions, simple execution, high chemoselectivity, good functional group tolerance, and a metal-free oxidation process.