The Rh(III)-catalyzed asymmetric reduction of α-trifluoromethyl ketones through transfer hydrogenation was developed under mild conditions to access a series of enantioenriched cistrifluoromethyl alcohols via a dynamic kinetic resolution process. The reaction was efficiently performed in the green solvent 2-MeTHF with HCO 2 H/Et 3 N (1 : 1) as the hydrogen source. High yields, alongside excellent diastereo-and enantioselectivities were obtained for the synthesis of CF 3 -chromanol, CF 3 -indanol and CF 3 -tetralol derivatives.