Treatment of α, β-unsaturated ketones and fluoroalkyl halides with Et2Zn in the presence of RhCl (PPh3) 3 gave novel reductive fluoroalkylation products at the α-position of α, β- unsaturated ketones in moderate to good yields. The rhodium hydride complex derived from Et2Zn and Rh catalyst seems to have played an important role in this reaction.