A chiral Ir-catalyzed reaction of α-aryl-α,β-unsaturated amides with β-substituted acrylates proceeded to give formal conjugate adducts in high yield and ee (up to 99% yield and up to 95% ee). This is the first example of the enantioselective cross-coupling of two different electron-deficient alkenes via vinylic sp2 C-H activation, and polyfunctionalized chiral compounds were obtained.