We have developed an unprecedented electrondonor-controlled divergent reaction between N-alkylsulfonylated acrylamides and Br−R F , facilitated by an electron donor−acceptor (EDA) complex, for the synthesis of fluorine-containing oxindoles and amides. Key to this divergent transformation is the EDA complex generation by altering electron donors. This approach has several advantages, such as broad substrate scope, being metalcatalyst-and photocatalyst-free, and having good functional group tolerance.