A catalytic amount of Pd(OAc)2 was successfully applied for the generation of enamines from various tertiary amines under oxidative conditions. As a synthetic application, the generated enamines were used for 1,4‐conjugate addition reactions with fluoroalkylated olefins. Thus, a catalytic amount of Pd(OAc)2 was added to a mixture of tertiary amines and fluoroalkylated olefins in N,N,‐dimethylacetamide in air, and the corresponding 1,4‐adducts were obtained in moderate to good yields for a variety of substrates. This unique reaction can allow readily available tertiary amines to be used as nucleophilic C2 synthons and is an alternative synthetic protocol for the hydroformylmethylation of olefins.