We have developed an unprecedented electron-donor-controlled divergent reaction between N-alkylsulfonylated acrylamides and Br-RF, 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 metal-catalyst- and photocatalyst-free, and having good functional group tolerance.