Employing the methyl β-perfluoroalkylpropionate as the Michael acceptor, an efficient approach for the synthesis of perfluoroalkylated pyrrolidine-fused coumarins has been achieved. A tandem reaction involving [3 + 2] cycloaddition and intramolecular transesterification was proposed for the mechanism. The enhanced electrophilicity resulting from the strong electron-withdrawing ability of the perfluoroalkyl group was crucial for this tandem reaction.