A new organocatalytic asymmetric Michael addition reaction by cleavage of carbon‐carbon bonds through a mild release of trifluoroacetate has been developed. The reported method generates the decarboxylated γ‐nitro‐α‐fluorocarbonyl products with excellent enantioselectivies (up to 98% ee) and good diastereoselectivies (up to 20:1 dr).