A simple, efficient, and mild method for defluorination and functionalization of 3,3,3-trifluoro carbonyl compounds has been developed. In the present method, Cs₂CO₃ can easily convert α-trifluoromethyl esters, amides, and ketones into β,β-S-, O- and/or N-substituted α,β-unsaturated carbonyl compounds in the presence of N-, O-, and S-nucleophiles with moderate to excellent yields, and furthermore, this transformation with α-trifluoromethyl ester and a series of 2-aminophenols can result in benzooxazoles in good yields.