The introduction of the CF3 unit is a common strategy for modifying pharmacokinetic properties and slowing metabolic degradation in medicinal chemistry. A catalytic and enantioselective addition of alpha-CF3 enolates allows for expeditious access to functionalized chiral building blocks with CF3-containing stereogenicity. To date, alpha-CF3 enolates have been a less explored class of nucleophiles because of rapid defluorination. The present study reveals that a designed alpha-CF3 amide enables a direct asymmetric Mannich-type reaction in a cooperative catalytic system.