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An unprecedented copper-catalyzed trifluoromethylation-initiated radical 1,2-aryl migration in α,α-diaryl allylic alcohols has been disclosed, which allowed access to a variety of α-aryl β-trifluoromethyl ketones.The migratory aptitude on unsymmetrical substrates supports the trifluoromethyl radical mechanism, which was further confirmed by DFT calculations.